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Indazoles and Condensed Types
Indazole reacts with potassium cyanate and acetic acid in ether to give indazole-2-carboxamide (m.p. 132-133") in poor yield. Heated above i ts melting point, the amide isomerizes to indazole-l-carbox- amide (m.p. 155').356 1-Carboxylic acid esters of indazole and some of i ts homologs have been prepared by reaction of the alcohol with in- dazole-1-carboxylic acid chloride, obtained from indazole and phos- gene.357,35* They can also be obtained from o-aminobenzaldoxime according to Equation 46.359
Other than those from indazole itself, the following esters of 2-car- boxylic acids have been made: ethyl 7-nitro-5-methylindazole-2-car- boxylate, 359 ethyl 7-amino- 5-methylindazole-2-carboxylate, methyl 3-phenylindazole-2-carboxylate,360 ethyl 3-phenylindazole-2- ~arboxyla te ,~60 and the methyl and ethyl es ters of 3-methylindazole- 2-carboxylic acid. 3 6 1
CH=NOCOOR A
NHCOOR I kOOR
(46)
Indazole-3-carboxylic acid crystallizes in needles from dilute alcohol and melts at 258-259" with decomposition. It can be prepared by treat- ment of isatin at a low temperature with nitrous acid, followed by re- duction (Equation 47),362-364 The acid is also obtainable f rom its nitrile, prepared from o -aminobenzonitrile by diazotization, 365-367 and by direct carbonation of indazole.210 The acid is decarboxylated above its melting point to give inda~ole .36~ It can be esterified directly;
fl
the methyl and ethyl es ters melt at 168-169" and 136-137" respect- ively.362 The ethyl es ter appears to be dimeric in naphthalene solu- tion (see Section II).368 The benzyl thiolester, obtained directly, mel ts at 165-166O.369 Indazole-3-carboxylic acid gives two substances with thionyl chloride, but neither of these appears to be a true acid chloride. The mixture, however, yields the amide3'0 and various substituted amides when treated with ammonia or the appropriate amine. 364, 3 6 9 - 3 7 l The dimethylamide has been used in the synthesis of the indazole analog of tryptophan.364 The hydrazide and some of its derivatives have been reported to have anorexigenic The bromination of indazole- 3-carboxylic acid yields the 5-bromo derivative (m.p. 305-306").373
341
Chapter 10
Indazole-3-carboxylic acid is difficult to alkylate, but the 1-methyl compound results when it is heated with sodium and methyl i0dide.~63 When indazole-3-carboxylic acid is heated with acetyl chloride or anhydride, a substance results which is believed to have a diketopiper- azine-like structure (46).374
Indazole-3-carbonitrile is prepared by dehydration of the amide.375 It nitrates in the 5 -pos i t i 0n~5~ and behaves normally in most of i ts reactions. It methylates readily,366 as do the es te rs of indazole-3- carboxylic acid, which have been methylated, 363 benzylated, 355 allyl- ated, 3'6 carbomethoxylated, 376 and acetylated. 373 The methyl ester has been reduced to 3-indazolylcarbinol with lithium aluminum hy- dride ,364
46
A number of other indazole-3-carboxylic acids have been reported. For the most part, they have been made by one of two processes: alkyl- ation of preformed acids or esters, 3559363.377 o r by treatment with alkali of the esters of 2, 4-dinitrophenylglyoxylic acid phenylhydra- z ~ n e s . ~ ~ ~ - ? a ~ By this latter method, a number of 6-nitro-1-arylind- azole-3-carboxylic acids have been prepared (Equation 48). These acids a re useful intermediates, since the amino compound, readily obtained by reduction, undergoes the usual diazotization and replace- ment reactions. For example, 1 -arylindazole-3-carboxylic acids can be obtained in this ~ a y . 3 ~ 9 It may be mentioned that these acids pro- vide a source for 3-indazole ketones, since they can be converted into acid chlorides, which wil l undergo the Friedel-Crafts reaction.379 Other ketones have been obtained by the reaction of indazole-3-car- bonitriles with Grignard reagents.3759383
Ar
342
Indazoles and Condensed Types
A few other indazole-3-carboxylic acids have been prepared by special methods. Thus, 5-methylindazole-3-carboxylic acid has been obtained from 5-methylisatin as in Equation 47.3C2 2-Methylindazole- 3-carboxylic acid has been made by heating 1 - (N-methylacetamido)-3- isatoxime with 50% sulfuric acid (Equation 49).384 2-Arylindazole-3- carboxylic acids have been obtained by hydrolyses of their nitr i les, obtained by reduction of 3-cyanoindazole- 1 -oxides,3 85,386 which are discussed in Section XIII. It has been reported that the reaction of diacetylyohimbine with nitric acid yields 6-nitroindazole - 3-carboxylic acid.377
Although there would not appear to be any especial difficulty involved in their preparation, no indazoles containing carboxyl groups in the carbocyclic ring a re known. 4-Cyanoindazole, however, has been ob- tained from the corresponding amine by way of the Sandmeyer reac- t i0n.38~ Hydrolysis should produce the acid, and it would be expected that other carboxylic acids could be produced in a similar way, since numerous aminoindazoles a re known.
47
Some side chain acids of indazole are known. Most of them have been prepared by alkylation using a-bromo esters or acids. The treatment of indazole with sodium and ethyl bromoacetate affords ethyl-2-inda- zole acetate. However, heated with the bromoester alone, indazole yields both the 1- and 2-substituted esters.388 Either procedure with ethyl a-bromopropionate affords both esters. In all of these cases the indazole es ters can be ~ a p o n i f i e d . ~ 8 8 p -(2-Indazolyl)propionic acid (47) results directly when indazole is heated with p -bromopropionic acid.388 p -(1 -Indazolyl)propionic acid (48) is obtained by the hydrolysis of i ts nitrile, produced by the addition of indazole to acrylonitrile.366 3 -C yanoindazole adds to ac rylonitrile similarly .366
o,̂ r N C H Z C H ~ C O ~ H
48
Indazole-3-acetic acid can be produced by the air oxidation of o - hydrazinocinnamic acid in the presence of alkali.389 The acid is read- ily esterified and the esters behave normally.390 It is easily nitro- sated and undergoes bromination in the 5-p0s i t ion .~g~ Chromic acid oxidizes the bromo acid to 5-bromoindazole-3-carboxylic acid where-
343
Chapter 10
C H ~ N C O C H ,
as indaeole-3-acetic acid is completely oxidized. The pyrolysis of the acid gives 3 -me thy l inda~o le .~ 89 1 -Ethylindazole-3-acetic acid has been prepared by a method analogous to that for indazole-3-acetic acid and i ts reactions a re similar.
y-(2-amino-4-nitrophenyl) butyric e s t e r (Equation 5 0 ) . 3 9 2
p -(6-Nitro-3-indazolyl)propionic acid is obtained by diazotization of
XI. AMINOINDAZOLES
No 1- or 2-aminoindazoles a r e known. A large number of those with amino groups in other positions have been reported, however. Since the methods of preparation and some of the reactions of the 3-amino- indazoles differ from those of the other aminoindazoles, they are con- sidered first .
The preparation of 3-aminoindazoles can be accomplished by the diazotization of o-aminobenzonitriles followed by r e d ~ c t i o n . ~ ~ ~ , ~ 9 3 Presumably, the reaction proceeds by way of the o-hydrazino compound. The preferred reducing agent is stannous chloride with hydrochloric acid. Other reducing agents, such as iron and acetic acid, zinc and acetic acid, and Raney nickel do not produce ring c l 0 s u r e . 3 9 ~ A second route to the 3-aminoindazoles uses reduction of azo-3-indazoles which
344
Indazoles and Condensed Types
are obtained by the coupling of indazoles having the 3-position open o r as by-products in the synthesis of indazoles from o-toluidines. Thus, if mesidine is diazotized and the diazonium solution warmed with alkali, there resul ts 5, 7-dimethylindazole and 2,4, 6-trimethylben- zeneazo-3-(5, 7-dimethylindazole) (Equation 51). Reduction of the l a t t e r affords 3 -amino- 5 ,7 -dimethylindazole.
Although the 3-aminoindazoles have chemical properties much like those of the aromatic amines generally, they differ in some respects . Diazotization yields chiefly a diazohydroxide (49),394)395 which is much more stable than most compounds of the type. They r eac t with acids to give "indazoletriazolenes" (Bamberger). These compounds have been formulated by Bamberger as containing a four-membered ring (501,396-398 but according to Hantzsch, they a r e diazo compounds (51).399 At any rate, they undergo the usual substitution and coupling reactions of diazonium solutions. Another unusual reaction of 3- aminoindazoles is their oxidation with strong oxidizing agents such as chromic acid, permanganate, hydrogen peroxide or persulfates. The products a r e benzotriazines such a s 52.3947396)397,400 Weaker oxidiz- ing agents, such as ferricyanide or air, a r e not effective.
H 49
+ -
50 51
3-Aminoindazole crystal l izes as white needles or leaves which melt a t 154" and a r e somewhat soluble in ~ a t e r . ~ 9 6 It can be p repa red by either general method discussed previo~sly.39~,393,396 It is basic (PK, = 3. 15)401 and readily fo rms sal ts with sulfuric, hydrochloric, oxalic, o r picric a ~ i d s . ~ 9 6 Silver nitrate or mercuric chloride f o r m "double salts ." Strong oxidizing agents produce the benzotriazine (52), but if air is bubbled through an alkaline solution, azo-3-indazole (53) results.402 The azo compound (m.p. 230") has weak acidic and basic properties. When treated with boiling aniline, it produces 3-aminoin- dazole and benzeneazo- 3 - indazole.
3-Aminoindazole undergoes acetylation with acetic anhydride and benzoylation with benzoyl chloride and sodium hydroxide. In both cases , diacylated products result.396 The diazotization of 3-aminoindazole produces an insoluble diazo hydroxide which melts at 128" with decom- position. Solution of the diazo hydroxide in acid and treatment with
345
Chapter 10
TABLE 7. Aminoindazoles by Reduction of Nitro Compounds
Indaz o le M.p. Reducing agent Yield Ref.
4 -amino - 151
4-amino- 5-methyl- 196
4-amino-6-methyl- 126
4 -amino- 7-methyl- 124
4-amino-7-acetamino- 160
4 -amino - 7 - acetamino - 5 -SO, H-
5-amino- 172
5 - amino - 4 - c hlor o - * 5-amino- 6-chloro-
5 -amino - 1 -methyl-
5-amino-2-methyl-
5-amino- 3-methyl-
5 -ammo - 4 -methyl-
5 - amino - 6 -methyl-
5-amino-6-methoxy-
5-amino- 1,3-diphenyl-
5-amino- 6-sulfonic acid
5-amino- 7-sulfonic acid
6- amino-
6-amino- 3-chloro-
6-amino- 5-chloro-
6-amino- 7-chloro-
6 -amino - 1 -methyl-
6-amino-2 -methyl-
181
183
149
178
127
105
233
197
224
165
2 10
210
206
209
203
184
193
184
173
130
169
FeSO, -NH, 409
H,(Ni) 92 293
FeSO, - NH , 440
H, (Nil 79 293
H,(Ni) 87 293
F e - HOAc 411
Fe-HOAc 411
FeSO, -NH, 7 5 412
H, (Nil 42 413,414
Zn-HC1 405
H, (Ni) 82 293
Sn-HC1 405
Fe-H,O 88 293
FeSO,-NH, 405
FeS0,-NH, 405
156
F e - HOAc 415
Fe-HOAc 415
Fe-H,O 90 293
SnC12-HC1 405
Fe-HOAc 411
Fe-HC1 411
H, (Ni) 81 401,414
Na, S 71 416
(NH,),S 417
(NH,),S; Sn-HC1 401
Fe-H,O 86 293
SnC 1, -HC 1 83 418
H, (Ni) 76 293
H,(Ni) 88 293
293
Na, S 40 293,416
H, (Ni) 7 5 293
Na, S 43 416
346
Indazoles and Condensed Types
TABLE 7 (cont.)
Indazole ~ ~~
M.p. Reducing agent Yield Ref.
165
157
6-amino- 3 -methyl 205
212
6-amino- 5-methyl- 242
165
6 -amino- 7 -methyl- 182
6-amino- l-phenyl- 150
6-amino-3-phenyl-
6-amino- 1, 3-diphenyl-
6-amino-7-p-tolyl- 200
6-amino-7-phenyl-4-acetyl- 228
6- amino- 1 -phenyl- 4 - carbomethoxy 11 5
6 -amino- 7 - sulf onic acid
7-amino - 156
7-amino- l-methyl- 135
7-amino-2-methyl- 73
7-amino- 3 -methyl- 203
7-amino- 5-methyl-
'I-amino- 5-chloro-
7-amino-4-chloro-5-methyl**
7-amino- 6 - methoxy-
7-amino-5-methyl- l-carbethoxy-
7- amino- 5 -methyl- 4 - benzamido - 7- amino -4 - sulfonic acid
5, 6-diamino-
172(d.) (NH,),S
166 (NH,),S
163 Fe-HC1
195 Sn-HC1
215(d.)
A1-Hg
209
280 SnC1,
60 419
81 293
409
91 293
156
71 420
71 293
a4 293
42 1
422
422
423
423
423
41 1
424
72 293
90 293
156
406
42 5
410
406
410
425
410
411
85 293
* Resul ts when 5-nitroindazole is reduced with tin and hydrochloric acid. Apparently an aniline rearrangement takes place a s well as reduction.
acid. An aniline rearrangement probably occurs here also. ** Results when 7-nitro-5-methylindazole is reduced with tin and hydrochloric
347
Chapter 10
alkali affords "indazoletriazolene," which melts a t 106". "Indazoletria- zolene" fo rms sal ts with chloroplatinic acid and with si lver nitrate and mercuric chloride. It couples with phenols, and if boiled with alcohol furnishes indazole. 3-Chloroindazole resul ts if an "indazoletria- zolene" solution is heated with hydrochloric acid, and 3-iodoindazole when potassium iodide is used,394,396, 398 Replacement by a cyano group has not been successful.394
?
52
53
3-Aminoindazole has been tested as an antimalarial, but has shown little promise.403 The p-aminobenzenesulfonyl derivative has been evaluated for its bactericidal value (see below).
Other 3-aminoindazoles whose properties appear to be s imilar to those of the parent compound a r e 5-methyl-3-aminoindazole (m.p. 190-191")394,398,402 and 5,7-dimethyl-3-aminoindazole (m.p. 133-134"),395,398,402 and 3-amin0-5-nitroindazole.~~~
Aminoindazoles having the functional group in the carbocyclic ring can usually be obtained by the reduction of the corresponding nitro compounds, which are readily available. A variety of reducing agents have been used (Table 7) and there appear to be no complications, ex- cept with tin and hydrochloric acid where an aniline rearrangement may occur,405,406 as shown in Equation 52.405 Other aminoindazoles can of course be obtained by substitution reactions with the aminoin- dazoles .
- Sn-HC1
O Z N W H H 2 N h H N (52)
The reactions of the 4-, 5 - , 6-, and 7-aminoindazoles are those of aromatic amines generally. They are rather weak bases (PKa for 6- aminoindazole = 3. 66)401 and although only slightly soluble in water, they are readily soluble in aqueous acids and may be reprecipitated f r o m such solutions by alkali, When 6-aminoindazole is treated with
348
Indazoles and Condensed Types
chlorine, there results a "ketochloride, I t whose structure is believed to be that represented by formula 54,407 the evidence being its reduc- tion to 4, 5, 7-trichloro-6-hydroxyindazole (55). If 6-aminoindazole is acetylated and then chlorinated, the normal reaction takes place, and 6-acetamino-7-chloroindazole is formed.408
55
The nitration of carbocyclic aminoindazoles leads to oxidation pro- ducts, but 7-benzamidoindazole can be nitrated in the 4 - p o ~ i t i o n . ~ l o The sulfonation of the carbocyclic aminoindazoles requires vigorous conditions, but can be accomplished in good yield. Thus 5-aminoinda- zole affords 5-aminoindazole-4-sulfonic acid with 100% sulfuric acid at 120"; 6-aminoindazole yields 6-aminoindazole-7-sulfonic acid with fuming sulfuric acid at 120" and 6-aminoindazole-5,7-disulfonic acid at 165". '7-Aminoindazole gives 7-aminoindazole-4-sulfonic acid in 95% yield with 100% sulfuric acid, and 7-amino-4,6-indazoledisulfonic acid in 89% yield with 65% 0 1 e u m . ~ ~ Interestingly, 7-nitroindazole yields a mixture of the same two sulfonic acids when it is treated with sodium bisulfite (Equation 53).411
The aminoindazoles undergo acetylation readily to yield solids which can serve as deri~atives.4~1,4~5,4~6~4~5,4~6 The primary group reac ts readily, sometimes merely when the amine is heated with acetic acid. A second acetylation can occur which involves the imino hydrogen of the pyrazole ring, but it requires more vigorous conditions. Benzoyla- tion also occurs readily under Schotten-Baummn conditions,406,410,425 and either a mono- o r dibenzoylated product can result. The following other amino derivatives have been made: chloroacetyl,425 carbamyl (with ~ r e a ) , ~ ~ ~ s a l i c y l , ~ ~ 7 , 428 and benzoylacetyl428 (patented as couplers in color-forming emulsions).
p-Aminobenzenesulfonamidoindazoles have been prepared by the reac- tion of p-acetamidobenzenesulfonyl chloride with the appropriate amino- indazole and hydrolysis of the prod~ct.4~49429,432 In nutrient media, these "sulfa drugs" appear to have about the same antibacterial activity
349
Chapter 10
as sulfathiazole o r sulfadiazine.433 In addition to 3-aminoindazole, 5- (p-aminobenzenesulfonamido)-indazole and 2-methyl-7- @ -diethyla- minoethy1amino)indazole have been tested as antimalarials, but none has shown p r0mise .40~ The arylation of 6-aminoindazole has been effected with 2, 4-dinitrochlorobenzene434 and with 2, 3-dihydroxy- naphthalene. 435
Other reactions which have been reported t o take place with some, at least, of the aminoindazoles are the conversion to hydroxyindazoles by heating with aqueous sulfuric a ~ i d , 4 ~ 9 the formation of Schiff b a ~ e s , 4 ~ 6 , 4 1 9 ~ 4 ~ 5 the replacement of the amino group by a thiocyano group with thiocyanogen, and the Skraup reaction,408 by means of which pyridoindazoles are obtained (Equation 54).
The diazotization of carbocyclic aminoindazoles proceeds normally, and the solutions behave pretty much as expected. Replacement by hy- drogen can be accomplished by use of hypophosphorous acid,413,423>424 e t h a n 0 1 , 4 ~ 6 > ~ 1 0 < 4 1 ~ or stannous sal ts . 409 Conversion to the phenol can be effected by heating the ~ o l u t i o n , ~ ~ 5 , ~ 1 6 > 4 1 7 > 4 2 6 or by the addition cf powdered g!ass,419,43e U I Lvric acid."S According to Fries and Tampke, 3 4 0 when 5-aminoindazole is diazotized and the solution heated, there results an azo compound (56) which is apparently produced by coupling of the newly formed phenol and unreacted diazonium compound.
56
The replacement of diazonium groups by halogen, 4 1 2 , 4 1 3 cyano, 409 and arsonic acid has been accomplished in the indazole series. The arsonic acids a re convertible &to arseno compound (Equa- tion 55). 437
Diazonium solutions from carbocyclic aminoindazoles couple with phenols t o give azo dyes.410,416,420)43*>43g,440 There is no informa- tion as to whether any a re used commercially. The aminoindazoles themselves react with diazonium solutions. If the reaction takes place in acid solution, an azo compound r e ~ ~ l t ~ ; ~ ~ ~ ~ ~ ~ ~ ~ 4 4 ~ in alkaline solu-
350
Indazoles and Condensed Types
(55) A s = A s
H ‘N
H H 2 0 3 A s
H
tion, an azoamino compound is produced (Equation 56) .4l9 A number of indazole dyes a r e metalizable and have been ~ a t e n t e d . 4 4 ~ - 4 4 8 Certain indazole dyes seem to be especially suited for acrylic fibers.449-453
A T N=NNH a H2Nw (56)
H H N = N A r
W. INDAZOLESULFONIC ACIDS
Because of their considerable solubility in water and lack of sha rp melting points, the indazolesulfonic acids a re difficult to character ize and there are contradictory reports in the literature. Indazole-4-sul- fonic acid has been prepared by the sulfonation of 7-aminoindazole and removal of the amino group via the diazonium salt.454 With phosphorus pentachloride it produces the sulfonyl chloride, m.p. 119-120”.
Indazole- 5-sulfonic acid has been obtained indirectly by the synthesis shown in Equation 57.454
NHCOCH3 NHCOCH, NHCOCH, H
NH2
351
Chapter 10
Indazole-6-sulfonic acid has been prepared f rom 5,6-dinitroindazole as shown by Equation 58. The disulfide 57 upon treatment with chlorine yields a mixture of 5-nitroindazole-6-sulfonyl chloride and 3-chloro- 5-nitroindazole - 6 - sulfonyl chloride, According to Petitcolas and Sureau,454 the sulfonation of indazole yields the 7-sulfonic acid, but von Auwers and Kleiner incline toward the 5-sulfonic acid structure.455 All of the indazolesulfonic acids so far discussed yield the co r re s - ponding hydroxy compound when heated with sodium o r potassium hy- droxide, 4549 455
The diazotization of o -aminobenzophenone followed by treatment with sodium sulfite yields chiefly 3-phenyl-2-hydroxyindazole, but there is a i so produced a small amount of sodium 3-phenylindazole -2-sulfon- ate.456 Acidification of an aqueous solution of this substance yields a "sulfonoxide" written by von Auwers as 58 but probably better r ep re - sented by the inner salt formula 59. The same compound resul ts if 3-phenylindazole is treated with ethyl chlorosulfonate. 456 An analogous substance has been obtained from 3-methylindazole-2-sulfonic acid.
Among the other indazolesulfonic acids that have been described a r e two 2-phenyl- ? -indazolesulfonic acids,457 various nitroindazolesul- fonic acids,454)458 some hydroxy sulfonic a ~ i d ~ , ~ 6 ~ ~ ~ ~ ~ j ~ ~ ~ , ~ 5 ~ j ~ 6 ~ and a number of aminoindazolesulfonic acids.160j293, 454)460 ,461
58 59
Xm. INDAZOLES OF BIOCHEMICAL INTEREST
The indazoles may be regarded as a z a analogs of the indoles. A num- b e r of such analogs of compounds of biochemical interest have been
352
Indazoles and Condensed Types
synthesized ostensibly for their possible antimetabolite propert ies . These include the indazole analogs of tryptophan,304 6-methyltrypto- phan,462 tryptamine,463 and serotonin.462-463 It appears that the indazole analog of tryptophan (tryptazan) interferes with the proper growth of certain yeasts4e6-4G9 and certain mutants of E. coli. 4 7 0 9 411 Effects on other organisms have also been d e s ~ r i b e d . 4 7 ~ - 4 7 5 Indazyl- acetic acid has growth-regulating properties like i ts indole a n a l 0 g . 4 ~ ~
XIV. INDAZOLE-1-OXIDES
A few indazole-1-oxides a r e known. The proof of structure depends upon the mode of synthesis and the fact that they may be reducedreadily to known indazoles. A number of closely allied methods have been used to prepare these compounds. o -Nitromandelonitrile, treated with an aromatic amine and a t race of sodium acetate produces 2-aryl-3-cyano- indazole-1-oxides (Equation 59).477 The same compounds can be ob-
C N
tained from o -nitrobenzaldehyde, the amine hydrochloride and potassium cyanide,477 or by way of the anil as shown in Equation 60.478 Alter- nately, the Schiff base in alcohol solution can be treated with potassium cyanide and acetic acid.480 According to Tanasescu and Tanasescu, the
reaction of ethyl o -nitro-phenylacetate with p - nitrosodimethylaniline in the presence of sodium carbonate or sodium phosphate yields ethyl 2-(p-dimethylaminophenyl)indazole-l-oxide-3-carboxylate. If the reaction proceeds as given by Equation 61, the nitroso compound must serve also as a reducing agent.48l
353
Chapter 10
3-Hydroxy-2-arylindazole oxides can be obtained from Schiff bases (Equation 62).482-484 The hydroxyl group r eac t s to form silver sal ts , which a r e readily convertible into ethyl e the r s by heating with ethyl iodide.
(62)
& H=NCeH5 N a 2 C 0 3 & r C s H 5
O2N
1 O2N NO2
0
Some of the indazole oxides have been reduced to indazoles by means of phosphorus trichloride,478 iron and hydrochloric acid,478 zinc and acetic acid477 or zinc and ethan01.48~ Chromic acid oxidation converts 3 -cyano-2-phenylindazole oxide into an azoxybenzenecarboxylic acid.478 This oxidation has been employed to establish the s t ructures of certain
d , 0 2 0 H "C,H,
1 0
60
azoxy c0mpounds.~79 The same cyano compound yields a sulfuric acid (60)) which reduction with iron and hydrochloric acid converts to o- aminobenzaniline (Equation 63).478 Hydrolysis of the sulfuric acid with hydrochloric acid furnishes a compound believed to be 2-phenylindazole- 1-oxide, which can also be reduced to o - a m i n o b e n ~ a n i l i d e . ~ ~ ~
354
Indazoles and Condensed Types
L 0
XV. 3H-INDAZOLES (RING INDEX 1211)
3-H-Indazole (indiazole; indiazene; 61) is unknown, but a number of derivatives have been prepared. Certain substances obtainable by treatment of o-aminobenzaldoxime with nitrous acid have been de- scribed as indiazone oximes (62). The following examples have been
61 62
reported: indiazone oxime (m.p. 160-160. 5°),485 5,7-dimethylindiazone oxime (m.p. 180"),486 4, 7-dichloroindiazone oxime (m.p. 166"),486 4, 7(? ) -dibromoindiazone oxime (76"), 486 and 6 -hydroxy - 7- methoxy- indiazone oxime.487 These substances a re yellow, and upon t reatment with alkalies they yield o-a~idobenzaldehydes.~85 Treatment with acid produces a mixture of o -aminobenzaldehyde and o -hydroxybenzalde- h ~ d e . 4 ~ 6 Meisenheimer488 has pointed out that certain benzotriazine oxides (62a) have properties closely analogous to those of the indiazone oximes. The benzotriazine formula also explains more readily the easy conversion of these compounds to o -azidobenzaldehydes.
62a
If indazole is heated with benzaldehyde and zinc chloride a t loo", a solid (m.p. 140-141"), believed to be benzalindiazole (63) results.489 A number of spiro compounds, such as 64, which a r e formally indiazole derivatives a r e not considered in this section.
355
Chapter 10
HC6H5 05 63
& N
64
The coupling reaction between indazole and diazonium solutions leads to products which may be indiazole d e r i v a t i v e ~ , ~ ~ ~ - 4 9 ~ but there is insufficient information to distinguish among the three possible for - mulas 65,66, and 67.
H 65 66 67
XVL INDAZOLONES
Indazolone itself can be represented by Formula 68, but many com- pounds referred tn as indazolones how phenolic properties. Such CCE-
68 69 70
pounds a re probably best considered tautomers involving two o r more s t ructures such as 68,69 and 70.4939 4 g 4 The phenol formula 69 may predominate.495 Ionic s t ructures probably contribute.496 In some instances, existence of two compounds of presumably the same s t ruc- t u re has led to the suggestion that they a r e the indazolone and a hydroxyindazole. Similar considerations hold for 3-aminoindazoles which may be regarded a s iminoindazoles (71). Although they are listed as such in Beilstein, their reactions resemble more closely those of aromatic amines, and they have been t reated as such (Section XI). Some few known indazolones possess two substituents in the pyrazole ring (72) so that tautomerism is unlikely.
71 356 72
Indazoles and Condensed Types
The f i r s t preparation of indazolone was by Emil Fischer who obtained it by heating o-hydrazinobenzoic acid (Equation 64).497 It was la te r
NHNH2 (64) H
found that for the preparation of indazolones generally, the s a m e end could be accomplished by heating the dry hydrochloride with phosphorus oxychloride498 o r merely by boiling an acid solution of the hydra- zine.499-502 Sometimes the indazolone is formed spontaneously. 5009 503 Thus, heating 2-chloro-3, 5-dinitrobenzoic acid with hydrazine hydrate gives 5, 7-dinitroindazolone (Equation 65).504 o-Hydrazino e s t e r s can
0 O Z N a : )
(65) H
c1 I H
NO2
be maae to close rings ~ i m i l a r l y . ~ ~ 5 - 5 0 8 In isolated instances, indazo- lones have been prepared by the pyrolysis of hydrazinium salicyl- ate, 509 heating salicylhydrazides, 5 0 9 9 510 heating anthranilic acid hydrazides,5O9, 510, 511 the diazotization of anthranilic acid hydrazides, 513 and the treatment of o-carboxyphenylhydrazones with concentrated sulfuric acid (Equation 66). 514
H
1-Substituted indazolones can be prepared by the decomposition- rearrangement of azides of carbamic acids.515, 5 1 6 For example, heating N-phenyl-N-ethylcarbamic acid azide in xylene for 6 hours a t the boiling point provides 1-ethylindazolone (Equation 67) in 68%
yield. 515 1-Substituted indazolones a r e also formed when unsymmet- rically substituted hydrazines a r e heated with urea (Equation 68).5l7 2-Arylindazolones have been prepared by the treatment of hydrazo-
357
Chapter 10
R
benzene-o -carboxylic acids with phosphorus oxychloride in pyridine5I8 o r acetic anhydrides' o r by treatment of azobenzene-o-carboxylic acids with phosphorus pentachloride, 520-523 o r by heating azobenzene- 2 -a ldehyde~ ,5~1 , 5247 S25 and f rom azobenzenes and carbon monoxide with a cobalt carbonyl ~ a t a l y s t . 5 2 6 - 5 ~ ~ The preparation of indazolones is summarized in Table 8. Section IX should also be consulted for the preparation of 3-hydroxyindazoles.
The indazolone a r e yellowish solids most of which melt with decom- position. They a r e amphoteric, being soluble in sodium carbonate and ammonia s o l u t i o n s . ~ O O ~ 523 The basic function is weaker,523 but some hydrochlorides are known, 5169 531 and well-defined picrates have been obtained. 5 0 2 7 517 They have been t i trated potentiometrically in alcohol with sodium procedures and the product appears to be the 0-methyl e t h e 1 - , 5 ~ ~ ) 533, 534 although in one instance the AT-methyl ether has been reported. 513 B e n z o y l a t i o n ~ ~ ~ ~ , 5137 533 and acetylations506, 5317 533 have been performed and both mono and disubstituted products result. Either phosphorus oxychloride502, 5 1 2 , 503 or phosphorus pentachlo- ride534 produces the 3-chloroindazole, but the latter reagent may also cause chlorination. 2-Arylindazolones are converted by strong oxidizing agents such as nitric acid, chromic acid, sodium hypochlor - i te o r potassium permanganate into azobenzene-o-carboxylic acids. 520-5239 533 A number of nitroindazolones have been reduced to the corresponding amines. 5009 506, S o 7
Indazolone crystallizes from alcohol as tablets o r needles which have no t rue melting point. The decomposition point has been reported at f rom 242" to 249". It can be prepared by most of the methods previously mentioned but best from o-hydrazinobenzoic a ~ i d . 5 0 ~ It is weakly amphoteric and is soluble in aqueous sodium hydroxide. 512 Indazolone undergoes nitrosation readily. 5 l 2 It r eac t s with Tollens' 1 - e a g e n t 4 ~ ~ but not with Fehling's solution.497, 4 9 8 It gives a deep-red solution which probably contains the azo compound with lead acetate.535 Acety- lation at room temperature affords the 2-acetyl derivative (m.p. 188")409 but a t a higher temperature, the 1, 2-diacetyl derivative (m.p. 112")396, 423 results. The Schotten-Baumann reaction affords the 0 -benzoate519 or a dibenzoyl derivative.499 The 1-carbomethoxy and 1-carbethoxy derivatives a r e obtained when indazolone is treated with the appropriate chlorofomate and pyridine.499 Indazolone and phosphorus oxychloride in the presence of pyridine afford 3-chloroin- dazole in a yield of 70%.501 Indazolone has been stated to have analge- sic, sedative, and spasmolytic p r0pe r t i e s .5~6 Magenta color couplers obtained from indazolones have been described. 537-545
Some have been methylated by the usual
358
TA
BL
E 8
. In
daz
olo
nes
Pro
du
ct
Pre
p.
M.p
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. M
etho
d Y
ield
R
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Inda
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ne
5- c
hlo
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6-c
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lor o
-
4-n
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-
242(
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1
242-
244(
d.)
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249(
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1
247
1
206
5
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5
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6
275-
276
1
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45-4
9
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499
498
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512
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527
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5-n
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5, 7
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-
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1,4
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thy
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thy
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-
5- c
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5,7
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275(
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305(
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300(
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240
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96
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504,
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515
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)
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5-m
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20
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Chapter 10
XVII. REDUCED INDAZOLES
Numerous partially reduced indazoles are theoretically capable of existence. Little is known of them, however, except for tetrahydroinda- zole 73 and its derivatives. Indeed, the location of the double bond or bonds in some of the partially reduced indazoles can not be considered settled.
The 4, 5,6,7-tetrahydroindazoles (cyclotetramethylenepyrazoles; cyclohexenopyrazoles) a r e best prepared by the reaction of a 2-substi- tuted cyclohexanone with a hydrazine. For example, 4, 5, 6, 7-tetrahy- droindazole itself is obtained in a 95% or better yield by the reaction of 2-hydroxymethylenecyclohexanone with hydrazine hydrate.s46 Other tetrahydroindazoles substituted in the carbocyclic ring can be obtained with the appropriately substituted cyclohexanone derivative. It is probable that the intermediate is a hydrazone, which should lead to a 2-substituted derivative when a substituted phenylhydrazine is employ- ed (Equation 69). However, the 1-derivatives appear in many cases to be the more stable, so that the products often constitute a mixture of the 1- and 2-derivatives, o r may consist entirely of the 1-substituted compound.547, 550 The enol acetate or benzoate may provide a more convenient start ing material than the free hydroxymethylene compound.
H
G O N N H R a I > R (69)
CHOH + H , N N H R ---+
Other methods of preparation for tetrahydroindazoles that have been employed less generally a r e the ring closure of o-chlorocyclohexanone phenylhydrazone,551 the reaction of 2-chlorocyclohexenal with hydra- zine hydrate,sz2 the addition of diazomethane to cyclohexene, which gives tetrahydroindazole in very poor yield, 5S3 and the hydrogenation of indazoles with platinum in acetic acid.554
best obtained employing the directions of Ainsworth.546 It melts a t 84" and boils a t 151" (14 mm). It is easily soluble in the common or - ganic solvents and is steam-volatile with difficulty. It f o r m s a silver salt and a picrate which melts at 155-156". It undergoes the reactions described in the following paragraph.
Tetrahydroindazole was first prepared by Wallach555 but is probably
362
Indazoles and Condensed Types
The 4, 5,6,7-tetrahydroindazoles are dehydrogenated by sulfur to yield indazoles.556 Migration of an alkyl group may occur. Catalytic dehydrogenation (palladium on charcoal) seems superior. 546, 547 Tetrahydroindazoles having imino hydrogen undergo alkylation readily. The preferred reagent is a halide with an alkoxide a s an acid acceptor, though the alkyl halide alone, with heating, has also proved success - f ~ 1 . 5 ~ 8 9 549 Usually both 1- and 2-alkylated products a r e obtained. They have been most commonly separated by fractional crystall ization of the picrates o r perchlorates. Most of the alkylated tetrahydroinda- zoles a r e liquids. Various of their physical properties have been re- corded.558 N-Alkylated tetrahydroindazoles undergo further reaction with alkyl halides to yield tetrahydroindazolium ~ a l t s . 5 ~ ~ ) 559 Pyroly- sis of the salts yields a mixture of N-alkyltetrahydroindazoles. 559 Acylation of tetrahydroindazoles occurs readily and produces both 1- and 2- substituted products.550, 560
Derivatives of tetrahydroindazole-3-carboxylic acids are easily made and are useful for synthetic purposes. The easiest entree to these com- pounds consists in the reaction of ethoxalylcyclohexanone with a hydra- zine (Equation 70).549, 5509 557 The ester group can be reduced by lithium aluminum hydride to the carbinol, which is an intermediate in the synthesis of the indazole analog of t r ~ p t a m i n e . 5 5 ~ The acid itself can be obtained by careful hydrolysis of the ester, or by direct synthe- sis, It melts a t 106-10'7". It and i t s homologs readily undergo decar- boxylation.549 The acids form mixed anhydrides on heating with acid chlorides. 5 6 l
(70) CzH5
COCOOCzH, + H2NNH2
N H
Little is known of other functional groups on the tetrahydroindazole nucleus. A few 3-amino compounds have been reported from react ions involving o-cyanocyclohexanones and semicarbazide or h y d r a ~ i n e . 5 6 ~ They fo rm azo compounds on mild oxidation but do not undergo the usual diazotization reaction.
The discovery that tetrahydroindazolones 74 have analgesic and antipyretic p r 0 p e r t i e s 5 6 ~ has spurred research with these compounds. They are usually prepared by the reaction of ethyl cyclohexanone-2-
363
Chapter 10
carboxylate with a substituted hydrazine and alkylation of the pro- duct.564-577 Though most investigators believe that the group present in the hydrazine finds itself in the 2-position in the product and that alkylation occurs in the 1-position, there is not complete agreement. Some of the indazolones yield molecular complexes with substituted barbituric a ~ i d s . 5 ~ ~ 3 579
Their spectral properties indicate that the indazolones a r e resonance hybrids to which ionic s t ructures are heavy contributors.580
Other than the tetrahydroindazoles mentioned above, few reduced indazoles having only one double bond have been reported and the information is fragmentary. A compound described as A l , 7a -hexa- hydroindazole has been obtained f rom 2-hydroxymethylcyclohexanone and h y d r a ~ i n e . 5 8 ~ The 3, 3,6-trimethvl derivative of this compound is
obtained from pulegone and hydrazine (Equation 71).5B2-584 Hexahy- droindazoles have been reported with the double bond in the 1, 2-posi- tion,s85 the 2,3-position,586 and the 3a, 7a-p0sit ion.58~
0 II
0 U CH,
f CH,N2 -> (72)
The reaction of certain catechol derivatives with diazohydrocarbons gives rise to partially reduced indazoles.588, 589 For example, 2-ace- toxy-2-methyl-3, 5-cyclohexadienone reacts with diazomethane as shown by equation 72.588 2-Hydroxy-2, 3, 5-trimethyl-3, 5-cyclohexa- dienone i s reported to react with diazomethane as given by Equation 73.589
give partially reduced indazoles.59°-5g3 For example, "C-acetyldi- methyldihydroresorcinol" reacts with phenylhydrazine as shown in equation 740590-591 The phenylhydrazone of the ketone may be the pro- d ~ c t . 5 ~ ~ 2-Acetyl-1, 3-cyclohexandione is reported to react as in Equation 75. 593 Similarly, 2-propionylcyclohexanone is described as
Similar compounds have been found to r eac t with phenylhydrazine to
364
Indazoles and Condensed Types
reacting with semicarbaxide to give a compound having s t ructure 75 o r 76. S g 4 Likewise, the reaction of the diester 77 with phenylhydrazine leads to a compound of unknown structure which, on treatment with alkali, furnishes a product whose structure is that represented by 7 8 . 5 9 5
78 C6H5
79
1, 3-Cyclohexadiene r eac t s with the C-chloro derivative of benzalde- hyde phenylhydrazone in the presence of triethylamine t o give the partially reduced indazole 79 in 75% yield.596 The compound affords a 79% yield of 1, 3-diphenylindazole on dehydrogenation with chlora- nil. 596
365
Chapter 10
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Hunziker, Lehner,Schindler, and Schmutz, Pharm.Acta Helv., 38,539 (1963).
Borsche and Wagner-Roemmich,&, 546,273 (1941).
Fuson and Hammann, J. Am. Chem. SOC., 74,1626 (1952).
-
-
136. Szmant and Harmuth, J. Am.'Chem.Soc., 81,962 (1959).
136a. Loudon and McCapra, J. Chem. SOC., 1959,1899.
137, Borsche and Diacont,&, 510,287 (1934).
138. Reid and Dietrich, Angew. Chem., 75,476 (1963);&, 666,135 (1963).
139. von Auwers and Frese,&, 58B, 1369 (1925).
140. Reich and Turkus, Bull. SOC. Chim. France, [4],21,107 (1917).
141. Reich and Gaigailian,=.,46,2380 (1913).
369
142.
143.
144.
145.
146.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
158.
159.
150.
161.
162.
163.
164.
165.
166.
167.
168.
169.
170.
171.
172.
173.
174.
175.
176.
177.
Chapter 10
Reich, Bull. SOC. Chim. France,[4] ,21,111 (1917).
Reich and Nicolaeva, Helv. Chim. Acta, 2, 84 (1919).
M e y e r , V . , B ~ . , 2 2 , 3 1 9 (1889).
Borsche and Butschli,&, 522,285 (1936).
Borsche,Ber. ,42,601 (1909).
von Auwers and Lange,-, 55B, 1139 (1922).
von Auwers and Demuth,&,451,282 (1927).
Fischer and Tafel ,&,227,303 (1885).
von Auwers and Lohr, J. Prakt. Chem., 108,297 (1924).
F r i e s and Roth,& 404, 81 (1914).
F r i e s and Weldert,&.,454,314 (1927).
F r i e s , Fabel, and Eckhardt,&, 550,31 (1941).
von Auwers and Kleiner, J. Prakt . C h e m . , l l 8 , 6 7 (1928).
Peti tcolas and Sureau, Bull. SOC. Chim. F rance , 1950,466; French Patent 1,005,327 (1952);*., 51,16561 (1957).
Sureau and Pernot, Bull. SOC. Chim. F rance , 1958,152.
Savitskaya, Tarasevich, and Shchukina, Zh. Obshch. Khim., 31,3255 (1961).
Paal and Li icker ,Ber . ,27,47 (1894).
Sureau and Mingasson, U.S. Patent 2,787,515, equivalent to Brit. Patent 775,829 (1957); C.A., 51,14279 (1957).
Dz+x,Eri! . Pa tmt 744,212 ( 1 9 5 6 ) ; ~ , 51,481 (1957).
von Auwers and Dusterdieck, J. Prakt . Chem., 118,53 (1928).
von Auwers, Sitz.-Ber.Ges. Bef.ges.Naturwiss.Marburg. 1925,137; C.A., 21,3982 (1927); Chem. Zentr., 1926, I, 2347
von Auwers and Allardt,=, 57B, 1098 (1924).
von Auwers and Lohr , J. Prakt .Chem., 108,297 (1924).
Pozharskii , Martsokha, and Siminov, Zh. Obshch. Khim., 33,1005 (1963).
Martsokha, Pozharskii , and Siminov, Zh. Obshch. Khim., 34,1317 (1964).
vonAuwers and DBesberg,%, 53B, 1179 (1920).
von Auwers and Schaich,=, 54B, 1738 (1921).
von Auwers and Pfuhl,=,58B, 1360 (1925).
von Auwers and Kleiner, J. Prakt . Chem., 118,67 (1928).
von Auwers and Allardt, Ber., 59B, 95 (1926).
von Auwers,Hiigel, and Ungemach,&, 527,291 (1937).
Barclay, Campbell, and Dodds, J. Chem. SOC., 1941,113.
von Auwers and S c h w e g l e r , E . , 53B, 1211 (1920).
von Auwers and Demuth,&,451,282 (1927).
Davies, J. Chem. SOC., 1955,2412.
Zhao and Shchukina, Zh. Obshch. Khim., 29,1012 (1959).
-
~
370
Indazoles and Condensed Types
178.
179.
180.
von Auwers, Ber. , 52B, 1330 (1919).
von Auwers, Ernecke, and Wolter,&,478, 154 (1930).
von Auwers and Hiittenes,=, 55B, 1112 (1922).
-
181. von Auwers and Dereser ,&, 53B, 1211 (1920).
182. von Auwers and StrBdter,=, 59B, 529 (1926).
183. Rousseau and Lindwall, J. Am. Chem. SOC., 72,3047 (1950).
184. von Auwers and Diiesberg,=., 53B, 1179 (1920).
185. von Auwers and Kleiner, J. Prakt . Chem., 118,67 (1928).
186. von Auwers and Pfuhl, Ber. , 58B, 1360 (1925).
187. von Auwers and Schaich,=., 54B, 1738 (1921).
188. von Auwers, Diisterdieck, and Kleiner,=.,GlB, 100 (1928).
189. Paal,%, 24, 959 (1891).
190. von Auwers and Hiittenes,&, 55B, 1112 (1922).
191. von Auwers and Lohr, J. P rak t .Chem., 108, 297 (1924).
192. von Auwers and Diisterdieck, J. Prakt. Chem., 118,53 (1928).
193. von Auwers and Allardt, B?, 57B, 1089 (1924).
194. Bamberger,&, 305,308 (1899).
195. von Auwers,=, 52B, 1330 (1919).
196. von Auwers and DCesberg,=., 53B, 1179 (1920).
197. von Auwers and Schwegler,=, 53B, 1211 (1920).
198. von Auwers and Lange,=.,55B, 1139 (1922).
199. Meisenheimer and Diedrich, B x . , 57B, 1715 (1924).
200. von Auwers, Ber . , 57B, 1723 (1924).
201. von Auwers and Allardt,&.,438,1 (1924).
202. von Auwers, Ber. , 58B, 2081 (1925).
203. Meisenheimer and Senn, Be r . , 59B, 199 (1926).
204. von Auwers, Ernecke, and Wolter,&, 478,154 (1930).
205. von Auwers and Demuth,&, 451,282 (1927).
206. von Auwers and Strijdter, Ber. , 59B, 529 (1926)
207. Zhao and Shchukina, Zh. Obshch. Khim., 29,3720 (1959).
208. Ziegler and Wolf, Monatsh. Chem., 93,1441 (1962).
209. von Auwers and F r e s e , B x . , 59B, 539 (1926).
210. Henkel e t C ie G.M.b.H., Bri t . Patent 816,531 (1959);C.A., 54, 1552 (1960).
211. Birkofer, Richter, and Ritter, Chem. Ber., 93, 2804 (1960).
212. Sureau and Pernot , Compt. rend. congr. intern. chim. ind., 31e, Liege, 1958, 2, 469;=.,54, 22587 (1960)
213. Fischer and Kuzel,&, 221, 261 (1883).
214. Fischer and Tafel , Ann., 227, 303 (1885).
-
-
- -
-
--
- 371
Chapter 10
von Auwers and DGesberg,=,53B, 1179 (1920).
Bamberger and von Goldberger,&, 305,339 (1899).
215.
216.
217.
218.
219.
220.
221.
222.
223.
224.
225.
226.
227.
228.
229.
230.
231.
232.
233.
234.
235.
236.
237.
238.
239.
240.
241.
242.
243.
244.
245.
246.
247.
248.
249.
Jensen and Friediger, Kgl. Danske Videnskab; Mat-fys.-Medd., 20, No. 2 0 , l (1943). -- C. A., 39, 2068 (1945); Chem. Zentr., 19441, 416.
Rousseau and Lindwall, J. Am. Chem. S O ~ . , 72,3047 (1950).
Thompson, Thesis, A Study of the Chemistry of Indazole, University of Illinois, 1949.
Kohlrausch and Seka, Ber., 71B, 1563 (1938); 73B, 162 (1940).
Stephenson, Org. Syntheses, Coll. Vol. III, 475 (1955).
Ainsworth, Org. Syntheses, Coll. Vol. IV, 536 (1963).
Huisgen and Bast, Org. Syntheses, 42,69 (1962).
Huisgen and Nakaten,&, 573,181 (1951).
Albert, Goldacre, and Phillips, J. Chem. SOC., 1948, 2240.
Jacobson and Huber, - Ber.,41,660 (1908).
Schad, - Ber., 26,216 (1893).
Fr ies , Fabel, and Eckhardt,&, 305, 339 (1899).
Bamberger and von Goldberger,&, 305,339 (1899).
Fischer and Seuffert, Ber., 34, 795 (1901). - Cambi and Canonica, Atti Accad. Nazl. Lincei, Rend., Classe Sci. Fis., Mat. e Nat., 20,17 (1956).
Siminov. Martsokha. and Pozharskii, Zh. Obshch. Khim., 33,1001 (1963).
ibid., 32, 2388 (1962).
-
Martsokha, Materialy-4-oi [Chetvertoe] Nauchn. Konf. Aspiriantov Sb, 106.
von Auwers and Dtesberg,=, 53B, 1179 (1920).
von Auwers and Kohlhaas,&,437,36 (1924).
von Auwers and von Meyenburg,=., 24,2370 (1891).
von Auwers,=,52B, 1330 (1919).
Bamberger and von Goldberger, &, 305,363 (1899).
Gabriel and Stelzner, B s , 29,303 (1896).
von Auwers and Lohr, J. Prakt. Chem., 108,297 (1924).
Bamberger, - Ann., 305, 289 (1899).
Bamberger, - Ann., 305,308 (1899).
von Auwers and Kleiner, J. Prakt. Chem., 118,67 (1928).
Borsche and Diacont,Ann., - 510,287 (1934).
Borsche and Biitschli,&, 522, 285 (1936).
von Auwers and Frese, B s , 58B, 1369 (1925).
Reich and Gaigailian, BE., 46B, 2380 (1913).
Paal and Krecke,=, 23,2634 (1890).
1962,
372
Indazoles and Condensed Types
Paal, - Ber., 27, 2897 (1894).
Paal and LGcker,=., 27,47 (1896).
Busch, - Ber., 27,2897 (1894).
Freundler, Bull. SOC. Chim. France, [3], 29,742 (1903).
Freundler, Bull. SOC. Chim. France, [3], 31,868 (1905).
Freundler, Compt. Rend., 138,1276 (1904).
Busch and Francis, J. Prakt. Chem., 51,272 (1895).
Paal and Fritzweiler, Ber., 25, 3167 (1895).
Busch and Francis, J. Prakt. Chem., 52,378 (1895).
Busch and Volkening, J. Prakt. Chem., 52,380 (1895).
Busch and Hartmann, J. Prakt. Chem., 52,404 (1895).
Paal and Fritzweiler,=, 25,3590 (1892).
Reich and Ghazarian, Bull. SOC. Chim., [4], 19, 259 (1916).
von Auwers and S t r a d t e r , E , 59B, 529 (1926).
von A u w e r s , g , 29,1255 (1896).
von Auwers and Huttenes,=., 55B, 1112 (1922).
Corbellini and Cecchi, Gazz. Chim. Ital., 63,489 (1933).
-
250.
251.
252.
253.
254.
255.
256.
257.
258.
259.
260.
261.
262.
263.
264.
265.
266.
267.
268.
269.
270.
271.
272.
273.
274.
275.
276.
277.
278.
279.
280.
281.
282.
283.
284.
285.
DziewBnski and Sternbach, Bull. Intern. Acad. Polonaise, Classe Sci. Math. Nat., 1935A, 333; C.A., - 30, 2972 (1936). - Borsche and Scriba, Ann., 540,83 (1939)
Schaum and Rorig, Z. Anorg. Chem., 132, 77 (1923).
von Auwers and Schaum, Ber., 62B, 1671 (1929).
Barben and Suschitzky, J. Chem. SOC., 1960,672.
von Auwers and Lange,%., 55B, 1139 (1922).
von Auwers, HGgel, and Ungemach,&, 527,291 (1937).
von Auwers and Lohr, J. Prakt. Chem., 108,297 (1924).
Fischer and Seuffert,=, 34,795 (1901).
Stephenson, Org. Syntheses, Coll. Vol. ID, 475 (1955).
Bamberger,=., 32,1773 (1899).
Bamberger and von Goldberger,&, 305,339 (1899).
Kenner and Curtis, J. Chem. SOC., 105, 2717 (1914).
Fischer and Tafel,&, 227,303 (1885).
von Auwers and Demuth,&.,451, 282 (1927).
von Auwers and Schwegler, =, 53B, 1211 (1920).
von Auwers, Ernecke, and Wolter,*,478,154 (1930).
Bamberger, - Ann., 305, 289 (1899).
Fischer and Blochmann, Ber., 35,2315 (1902).
__
-
- 373
Chapter 10
Freundler, Bull. SOC. Chim., [4], 9 , 778 (1911).
Freundler,Compt.Rend., 152,1256 (1911).
Barclay, Campbell, and Dodds, J. Chem. SOC., 1941,113.
Petitcolas and Sureau, Bull, SOC. Chim. France, 1950,466.
Freundler, Bull, SOC. Chim. France, [4], 9,735 (1911).
Pearman, J.Chem. SOC., 119,717 (1921).
Fr ies and Tampke,&,454,303 (1927).
Davies, J. Chem. SOC., 1955,2412.
N o e l t i n g , E , 37, 2556 (1904).
Zincke and Malkomesius,&, 339, 224 (1905).
Brand and Eisenmenger, J. Prakt. Chem., 87,487,498 (1913).
Borsche and Herbert,Ann., 451, 282 (1927).
von Auwers and Demuth,Ann.,451,282 (1927).
Barclay, Campbell, and Dodds, J. Chem. SOC., 1941,113.
von Auwers and Frese,=, 58B, 1369 (1925).
von Auwers and S c h w e g l e r , E . , 53B, 1211 (1920).
von Auwers and Kleiner, J. Prakt. Chem., 118,67 (1928)
__
286.
287.
288.
289.
290.
291.
292.
293.
294.
295.
296.
297.
298.
299.
300.
301.
302.
303.
304.
305.
306.
307.
308.
309.
310.
311.
312.
313.
314.
315.
316.
317.
318.
319.
Stauffer, U.S. Patent 2 497 917 (1950) to Eastman Kodak Co.; - C.A., 44, 9841 (1950).
Hanson and Richey, U.S. Patent 2 496 940 (1950) to Eastman Kodak Co.; C.A.,44,5747 (1950).
Passal, U.S. Patent 2,684,327 (1954);=, 48,10462 (1954).
Witt, Nolting, and G r a n d m o u g i n , s , 23,3635 (1890).
Fieser, J. Am. Chem. S O C . , ~ ~ , 1097 (1926).
Fr ies , Fabel, and Eckhardt, &, 550,31 (1941).
Petitcolas and Sureau, Bull. SOC. Chim. France, 1950,466.
Hahn and Just, Ber., 65B, 717 (1932).
-
- Flett, U.S. Patent 2 469 378 (1949) to Allied Chemical and Dye Gorp.;%, 43,6846 (1949).
Reich and G a i g a i l i a n , g , 46, 2380 (1913).
Sureau, Bull. SOC. Chim. France, 1956,622.
Kenner and Witham, J. Chem. SOC., 119,1053 (1921).
Vesely and Medvedeva Collection Czechoslav. Chem. Commun., 9, 176 (1937); C. - A,, 31, 5355 (1937).
Borche and Diacont,Ann., - 510,287 (1934).
Borsche and Scriba,+, 540,83 (1939).
von Auwers and Frese, BE, 59B, 539 (1926).
Gabriel and Stelzner,%, 29,303 (1896).
374
Indazoles and Condensed Types
320. Bamberger and Demuth,=, 35,1891 (1902).
321. Bamberger, Ber. , 55B, 3371 (1922).
322. von Auwers, Ber. , 29,1255 (1896).
323. von Auwers and Hiittenes,=., 55B, 1112 (1922).
324. von Auwers and Strijdter, B s . , 59B, 529 (1926).
325. DziewBnski and Sternbach, Bull. Intern. Acad, Polonaise, C las se Sci. Math. Nat., 1935A, 333; - C. A., 30,2972 (1 936).
326. Freundler, Compt. Rend., 142,1153 (1906).
327. Freundler, Compt. Rend., 143,909 (1906).
328. Freundler, Bull. SOC. Chim., [4], 9 , 735 (1911).
329. Freundler and de Laborderie, Bull. SOC. Chim., [4], 1 ,234 (1907).
330. Freundler, Compt. Rend., 152,1256 (1911).
331. Heller, Ber., 49, 2757 (1916).
332. Heller, Ber. , 55B, 2680 (1922).
333. Freundler, Bull. SOC. Chim., [4], 1, 228 (1907)
334. Freundler, Bull. SOC. Chim., [4],9, 778 (1911).
335. B a m b e r g e r , g , 4 4 , 1 9 6 6 (1911).
336. Arold, J. Prakt. Chem.,23, 329 (1964).
337. Heller, Ber. , 49, 546 (1916).
338. Carr6,Ann. Chim., [8], 19, 206 (1910).
339. Ca r r6 , Bull. SOC. Chim., [3], 35, 1275 (1906).
340. Carr6, Compt. Rend., 143,54 (1906).
341. Wessely, Schinzel, Spiteller, and Klezl, Monatsh. Chem., 90,96 (1959).
342. von Auwers and Kleiner, J. Prakt . Chem., 118,67 (1928).
343. F r i e s and Tampke,Ann., - 454,303 (1927).
344. F r i e s , Fabel, and Eckhardt,&, 550,31 (1941).
- -
- -
-
345.
346.
347.
348.
349.
350.
351.
352.
Spiteller and Wessely, Monatsh. Chem., 90, 660 (1959).
Witt, Nijlting, and Grandmougin, B s , 23, 2635 (1890).
F r i e s and Roth,&, 404,81 (1914).
Fieser , J . A m . Chem.Soc.,48,1097 (1926).
Zhao and Shchukina, Zh. Obshch. Khim., 29,3724 (1960).
Zincke and Kuchenbecker,&, 339, 235 (1905).
F r i e s and Weldert,&.,454,314 (1927).
Weygand and Henkel, B z . , 76B, 818 (1943).
353. Kovach and Barnes, J. Am. Chem. SOC., 76,1176 (1954).
354. Martsokha, Materialy-4-oi [Chetvertoi] Nauchn. Konf. Aspiriantov Sb, 1962, 106.
355. von Auwers and S c h a i c h , S , 54B, 1738 (1921).
375
Chapter 10
356. von Auwers and Frese,&.,450, 273 (1927).
357. von Auwers and A l l a r d t , s . , 4 3 8 , l (1924).
358. von Auwers and Demuth,&, 451,282 (1927).
359. von Auwers and Frese,=., 59B, 539 (1926).
360. von Auwers and Hiittenes,=., 55B, 1112 (1922).
361. von Auwers and Lohr , J. P rak t . Chem., 108,297 (1924)
362. Schad, - Ber. , 26, 216 (1893).
363. von Auwers and Dereser,=., 52B, 1340 (1919).
364. Syyder, Thompson, and Hinman, J. Am. Chem. SOC., 74, 2009 (1952).
365. Salkowski, - Ber. , 17,508 (1884).
366. Rousseau and Lindwall, J. Am. Chem. SOC., 72,3047(1950).
367. Pschor r and Hoppe,=., 43,2543 (1910).
368. Hayes and Hunter, J. Chem. SOC., 1941, l . 369. Hinman, Thesis , University oi Illinois, 1952.
370. Kochetkov and Dudykina, Zh. Obshch. Khim., 31,201 (1961).
371. Dudykina and Kochetkov, Zh. Obshch. Khim., 32,81 (1962).
372. Kirchner, U. S. Patent 3,007,938 (1959).
373. von Auwers and Lange, B z . , 55B, 1139 (1922).
374. von Auwers and Cauer,=., 61B, 2402 (1928).
375. P izz i and Ronchi. Gazz. Chim. Ital, 93, 3 (1963).
376. von Auwers and StrEdter,=., 59B, 529 (1926).
377. Hahn and Just , Ber. , - 65B, 717 (1932).
378. Borsche and Diacont,+,510,287 (1934).
379. Borsche and Bctschl i ,&E. , 522, 285 (1936).
380. V. Meyer,=., 22,319 (1889).
381. Dittrich and V. Meyer,Ann., - 264,129 (1891).
382. V. Meyer and SchulhEfer,&., 264,149 (1891).
383. Meisenheimer and D i e d r i c h , e , 57B, 1715 (1924).
384. Neber and Keppler, BE., 57B, 778 (1924).
385. Heller and Spielmeyer, - Ber . , 58B, 834 (1925).
386. von Auwers and Schwegler,%, 53B, 1211 (1920).
387. Tanasescu and Tanasescu,Bull. SOC. Chim., [5], 2,1016 (1935).
388. von Auwers and Allardt,=., 59B, 95 (1926).
389. Fischer and Tafel,Ann., 227,303 (1885).
390. Savitskaya and Shchukina, Zh. Obshch. Khim., 31,1015 (1961).
391. Ainsworth, J .Am.Chem. SOC., 80,967 (1958).
392. Re i s se r t and Grube, B ~ . , 4 2 , 3 7 1 6 (1909).
393. Kwartler and Lucas, J. Am. Chem. SOC., 65,1804 (1943).
-
376
Indazoles and Condensed Types
394. Bamberger, - Ann., 305, 289 (1899).
395. Bamberger,&, 305,308 (1899).
396. Bamberger and von Goldberger,&., 305,339 (1899).
397. Bamberger and von Goldberger,&., 305,363 (1899).
398. Bamberger, B x . , 32,1773 (1899).
399. Hantzsch, - Ber., 35, 888 (1902).
400. Bamberger and von G o l d b e r g e r , K . , 31,2636 (1898).
401. Albert, Goldacre and Phillips, J. Chem. SOC., 1948, 2240.
402. Bamberger and Wildi, Ber., 39,4276 (1906).
403. Wiselogle, Survey of Antimalarial Drugs, Vol. 11, Edwards Brothers , Ann Arbor, 1946.
404. Parnell, J. C hem. Soc., 1959, 2363.
405. Fr ies and Tampke, Ann., 454,303 (1927).
406. Gabriel and Stelzner,&., 29, 303 (1896).
407. Fr ies and Weldert, - Ann., 454, 314 (1927).
408. Fr ies and Madjid, - Ann., 454, 311 (1927).
409. von Auwers and Schwegler,%, 53B, 1211 (1920).
410. British Patent 599 834, March 22, 1948; - C. A., 42, 7538 (1948).
411. Peticolas and Sureau, Bull. SOC. Chim. France, 1950,466.
412. von Auwers and Lange,%, 55B, 1139 (1922).
413. Himan, Thesis, University of Illinois, Urbana, Illinois, 1952.
414. Kwartler, U. S. Patent 2 478 048 to Winthrop-Stearns,August 2,1949;C. A., 44,3525 (1950).
-
415. Veselj. and Medvedeva, Collection Czechoslav. Chem. Commun., 9 ,176 (1937);=., 31, 5355 (1937).
416. von Auwers and Demuth, Ann., 451,282 (1927).
417. Witt, NElting, and G r a n d m o u g i n , z , 23,3635 (1890).
418. Fieser , J. Am.Chem. S O C . , ~ ~ , 1097 (1926).
419. Fabel, Thesis, University of Brunswick, Robert Noske, Leipzig, 1930.
420. Pearman, J. Chem. SOC., 119, 717 (1921).
421. Borsche and Diacont,&., 510,287 (1934).
422. Borsche and Scriba,&., 540,83 (1939).
423. Borsche and Biitschli, - Ann., 522, 85 (1936).
424. Noelting, - Ber., 37, 2556 (1904).
425. von Auwers and Frese,Ber,, 59B, 539 (1926).
426. Witt,Noelting, and Grandmougin, K, 25,3149 (1892).
427. Van Allan, J. Am. Chem. SOC., 69, 2913 (1947).
428. Brit. Patent 577,804 to Kodak Ltd., March 31,1946. C.A., 41, 1568 (1947).
429. Tillotson, U. S. Patent 2 374 791, May 1,1945; - C.A.,40,1636 (1946).
-
-
377
Chapter 10
Swiss Patent 242,054 to Aktien-Gesellschaft vom B. Siegfried, Sept., 1946; - C. A.,43,7966 (1949).
Rajagopalan, Current Science (India), 11,146 (1942);=., 36,6511 (1942).
Rajagopalan, Proc. Indian Acad. Sci., 18A, 100 (1943); C. A,, 38, 730 (1944). Lawrence and Goetchius, Proc. SOC. Exptl. Biol. Med., 58, 356 (1945).
German Patents 117,820 and 118,079 to Leopold Casella and Co.; Chem. Zentr., 1901, I, 488,551.
Kracker, German Patent 580,519, July 12,1933, to I.-G. Farbeindustrie; - C. A, , 28,1051 (1934).
Fries , Fabel, and Eckhardt, - Ann., 454,311 (1927).
Plazek and Neymanowna, Roczniki Chem., 12, 706 (1932); Chem. Zentr., 19331, 776.
CIBA Ltd., Brit. Patent 695, 330 (1953);C. - A.,48,4847 (1954).
Societ6 anon. de matieres colorantes e t produits chimiques Francolor, French Patent 981,432 (1951).
Peticolas, Sureau, Roe, and Develotte, U. S. Patent 2,675, 734 (1954). G., 49,1337 (1955).
430.
431.
432.
433.
434.
435.
436.
437.
438.
439.
440.
441.
442.
443.
444.
445.
446.
447.
448.
449.
450.
451.
452.
453.
454. 455.
456.
457.
458.
459.
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Davies and Legg, Brit. Patent 748,507 (1956); - C. A., 50,16115 (1956).
Davies and Legg, Brit. Patent 753,573 (1956); - C. A., 51, 7429 (1957).
Davies, Brit. Patent 747,871 (1956);%., 51, 8444 (1957).
Davies, Brit. Patent 760, 595 (1956); - C. A., 51,9168 (1957).
Davies, Brit. Patent 760, 710 (1956);%, 51,9168 (1957).
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Sureau and Kremer, French Patent 1, 211,449, (1960);-., 55,13863 (1961).
Sureau and Kremer, French Patent addition 77,666 (1962);=.,58,4671. (1963).
Sureau, Kremer, and Dupre, Belg. Patent 609,146 (1962);*, 59,1791 (1963).
Sureau, Mingasson, and Kremer, Belg. Patent 628,678 (1963); C. A., 61, 751 (1964).
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von Auwers and Kleiner, J. Prakt. Chem., 118,67 (1928).
von Auwers and HCttenes,=., 55B, 1112 (1922).
Paal and Lucker, - Ber., 27,447 (1894).
Zincke and Kuchenbecker,&, 339,235 (1905).
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-
378
Indazoles and Condensed Types
460. Peti tcolas and Sureau, French Patent 1,005,327 (1952);=., 57,16561 (1957).
461. Peti tcolas and Sureau, Bull. Soc. Chim. France, 1954,986.
462. Synder and Williams, J. Am. Chem. SOC., 76,1298 (1954).
463. Ainsworth, J .Am. Chem. SOC., 79, 5242 (1957).
464. Ainsworth, J .Am. Chem. SOC., 79,5245 (1957).
465. Ainsworth, J. Am, Chem. Soc., 80,965 (1958).
466. Halvorson, Spiegelmann, and Hinman, Arch. Biochem. Biophys., 55, 512 (1955).
467. Davie, Konigsberger, and Lipmann, Arch. Biochem. Biophys., 65, 21 (1956).
468. Halvorson and Jackson, J. Gen. Microbiol., 14, 26 (1956).
469. Sharon and Lipmann, Arch. Biochem. Biophys., 69, 219 (1957).
470. Pardee , Shore, and P res t ige , Biochim. Biophys. Acta, U, 406 (1956). 471. Browerman and YEas,Arch. Biochem. Biophys., 68,112 (1957).
472. Frieden, Westmark, and Schor, Arch. Biochem. Biophys., 92,176 (1961).
473. Durham and Mart in , Biochem. Biophys. Acta, 71,481 (1963).
474. Adler, J. Med. Chem., 6,480 (1963).
475. Lingens, 2. Physiol. Chem., 331,56 (1963).
476. Hellman, Sell , and Wittwer, Phyton (Buenos Aires) , 16,1 (1961); - C.A., 57, 5057 (1962).
477. Heller and Spielmeyer, B z , 58B, 834 (1925).
478. Reis se r t and Lemmer , B x . , 59B, 351 (1926). 479. Behr, J .Am.Chem. SOC., 76, 3672 (1954).
480. Akashi, C. A., 43, 7934 (1949); Bull. Inst. Phys. Chem. Research. (Tokyo), 20, 798 m)
481.
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488.
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Secareanu and Lupas, Bull. SOC. Chim. France, [5], 2,69 (1935)
Bamberger and Demuth,=., 34,1309 (1901)
Bamberger and Weiler, J. P rak t . Chem., 58,333 (1898).
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Meisenheimer, Senn, and Zimmerman, BE., 60,1736 (1927).
489.
490. Noelting, Be r . , - 37, 2556 (1904). 491.
Bamberger and von Goldberger,&, 305,339 (1899).
Bamberger and Wildi, B z , 39,4276 (1906).
492. Grandmougin and Freimann, J. Prakt . Chem., 78,384 (1908). 493. Pfannstiel and Ludde, Pha rm. Zentralhalle, 91,345 (1952); C. - A., 47, 7492
494. Serfass and Geppert , Monatsber.Deut. Akad. Wiss. Berlin, 4, 125 (1962); C. A., 59,4688 (1963). -
379
Chapter 10
Janssen, Proc. Intern. Meeting Mol. Spectry. , 4th, Bologna, 1959,2, 820 (1962).
O'Sullivan, J. Chem. SOC., 1960, 3278
Fischer , B x . , 13,697 (1880).
Fischer and Seuffert, B x . , 34, 795 (1901).
Heller and Jacobsohn,=,54B, 1107 (1921).
Pfannstiel and Janecke,=., 75B, 1096 (1942).
Stephenson, Org. Syntheses, 29, 54 (1949).
Fischer and Blochmann, B2,35,2315 (1902).
Gleu and Pfannstiel, J. Prak t . Chem., 146,129 (1936).
Purgotti and Contardi, Gazz. Chim. Ital., 32,I, 573 (1962).
Rupe, B z , 30,1097 (1897).
Kenner and Witham, J. Chem. SOC., 119,1053 (1921).
Kenner and Curt is , J. Chem. SOC., 105,2717 (1914).
Shunk and Wilds, J. Am. Chem. SOC., 71,3946 (1949).
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Thode, J. Prak t ,Chem. ,69 ,92 (1904). Heller and KEhler, Ber . , 56B, 1595 (1923).
Konig and Reisser t , B s , 32,782 (1899). Leonard, Boyd, and Herbrandson, J. Org. Chem., 12,47 (1947).
Stoll6, Nieland, and Merkle, J. P rak t . Chem., 116, 192 (1927).
Stollk, Nieland, and Merkle, J. Prakt . Chem., 117, 185 (1927).
Milrath, Monatsh., 29,909 (1908).
Freundler, Bull. SOC. Chim., [4], 9, 735 (1911).
Heller, Ber. ,49, - 2757 (1916).
Freundler, Compt. Rend., 142,1153 (1906).
Freundler, Compt. Rend., 143,909 (1906).
Freundler, Bull. SOC. Chim., [4],1, 228 (1907).
Freundler,Compt. Rend., 152, 1256 (1911).
Freundler and de Laborderie, Bull. SOC. Chim., [4], 1, 234 (1907).
Friedlznder and Lenk, - Ber. ,45,2085 (1912).
Murahashi and Horiie, Japanese Patent 8925 (1957);-., 52,14701 (1958).
Horiie, Nippon Kagaku Zasshi, 79,499 (1958);=., 54,4607 (1960).
Horiie, Nippon Kagaku Zasshi, 80,1038 (1959); C.., 55, 5510 (1961).
Murahashi and Horiie, U.S. Patent 2,949, 056 (1960);-., 55,1667 (1961). J.Am.Chem. SOC., 78,4816 (1956). Horiie and Murahashi, Bull. SOC. Chim. Japan, 33,88 (1960).
-
495.
496.
497.
498.
499.
500.
501.
502.
503.
504.
505.
506.
507.
508.
509.
510. 511.
512.
513. 514.
515.
516.
517.
518.
519.
520. 521.
522.
523.
5 24.
525.
526.
527.
528.
529.
530.
380
Indazoles and Condensed Types
531.
532.
533.
534.
535.
536.
537.
538.
539.
540.
541.
542.
543.
544.
545.
546.
547.
548.
549.
550.
551.
552.
553.
554.
555.
556.
557.
558.
559.
560.
561.
562.
563.
564.
565.
566.
Fischer,&., 212, 333 (1892).
Veibel, Kjaar , and Plejl, Acta Chem. Scand., 5,1283 (1951).
von Auwers and Hii t tenes ,Bx. , 55B, 1 1 2 (1922).
Freundler , Bull. SOC. Chim., [4], 9 , 778 (1911).
Ullman and Bartkus, Chem. Ind. (London), 1962,63.
Pfannstiel and Liidde, P h a r m . Zentralhalle, 91, 345 (1952); C.A., 47, 7492 (1953).
Jennen, Ind. Chim. Belge, 16,472 (1951);C. A., 46,6387 (1952).
Jennen, Mededel. Vlaam. Chem. Ver. , 18,43 (1956);C.A., 51,5094 (1957).
Jennen, U.S. Pa ten t 2,673,801 (1954);=., 48,9850 (1954).
Wooley, Bri t . Patent 729 505 (1955);C.A., - 50, 712 (1956).
Gevaert Photoproducten N.V., Belg. Patent 514,576 (1933);=., 51,17542 (1957).
MacDonald, Mirzon, and Woolley, Brit . Patent 875,470 (1958).
Webster and Brooker , U.S. Patent 2,961,317 (1960); - C.A., 55,6221 (1961).
Jennen and Eerdekens, U.S. Patent 2,964,402 (1960);=., 55,9129 (1961).
Ba r r , Henn, and Salminen, U.S. Patent 3,043, 694 (1962); C, 57, 16048 (1961).
Ainsworth, Org. Syntheses, Col. Vol. II, 536 (1963).
von Auwers, Buschmann, and Heidenreich, Ann,, - 435,277 (1924).
von Auwers, von Sass , and Wittekindt,Ann., - 444, 195 (1925).
von Auwers, Conrad, Ernecke, and Ottens,&, 469,57 (1929).
von Auwers and Wolter, J. P rak t . Chem., 126, 204 (1930).
Kuehne, Weaver, and F ranz , J. Org. Chem., 29,1582 (1964).
Schlager, Arch. Pha rm. , 296, 758 (1963).
Mousseron and Manon, Bull. SOC. Chim. France, 1949,392.
F r i e s , Fabel, and Eckhardt, Ann,, 550, 31 (1941).
Wallach, - Ann., 329,109 (1903).
Grandberg, Kost, and Yaguzhinskii, Zh. Obshch. Khim., 29,2537 (1959).
Ainsworth, J . A m . Chem. SOC., 79,5242 (1957).
von Auwers and Kohlhaas, &. ,437,36 (1924).
von Auwers, Conrad, and Ernecke,&., 469,82 (1929).
von Auwers,&, 453, 211 (1927).
von Auwers and Wolter, E., 63,479 (1930).
von Auwers, Bahr ,and Frese,&., 441,68 (1925).
Mannich, Arch. P h a r m . , 267, 699 (1929).
Dieckmann,&., 317, 27 (1901).
Rabe and Eke,&., 323,83 (1902).
Rabe and Rahm, - Ann., 3 3 2 , l (1904).
-
381
Chapter 10
567. Kstz and Hesse,Llnn., 342,306 (1905).
568. Dieckmann and von Fischer, Ber.,44,966 (1911).
569. Lee and Christiansen, J . Am. Pharm. Assoc., 25,691 (1936). 570. Bradfield, Jones, and Simonsen, J. Chem. Soc., 1936,1137.
571. Ruhkopf, - Ber., 70,939 (1937).
572. Lee, U.S. Patent 2,104,348 (1938); - C.A., 32,1869 (1938).
573. Ruhkopf and Mohs, German Patent 668,628 (1938);=., 33, 5131 (1939).
574. Ruhkopf, Ber., 72,1978 (1939).
575. Picard, Seymour, and Dyer, Chemist and Druggist, 140,150 (1943); Quart. J. Pharm. Pharmacol., 16, 264 (1943).
576. Mousseron, Bull. SOC. Chim. France, 1947,612.
577. Skaric, Skaric, Turjak-Zebrik, and Veksli, Croat. Chem. Acta, 34,75 (1962); - C .A . , 58,4539 (1963).
578. Ruhkopf, - Ber., 70,939 (1937).
579. Ruhkopf and Mohs,German Patent 659,221 (1938);=., 32,5582 (1938).
580. De Stevens, Halamandaris, Wenk, and Dorfman, J. Am. Chem. Soc., 81, 6292 (1959).
581. Olsen and Aalrust,&.,648., 29 (1961).
582. Kishner and Sawadowski, J. Russ. Phys. Chem. Soc., 43,1132 (1911); Chem. Zentr., 19121,1456.
583. Kishner, J. Russ. Phys. Chem. Soc., 44,165 (1912).
584. Sussc and Gireiiiitscii, - Ber. , 63,2209 ii53Oj.
585. Grewe and Bokranz, Chem.=, 88,491 (1955).
586. Dimroth and Laewitz,Chem. Ber., 81,242 (1948).
587. Pocar, Bianchetti, and Maiorana, Gazz. Chim. Ital., 93, 100 (1963).
588. Wessely, Schinzel, Spiteller, and Klezl, Monatsh. C hem., 90,96 (1959). 589. Spiteller, Schmidt, Budzikiewiez, and Wessely, Monatsh. Chem., 91,129
(1960).
590. Dieckmann and Stein,=., 37,3370 (1904). 591. Crossley and Renouf, J. Chem. SOC., 101,1524 (1912).
592. Wichterle,Prochfizka, and Hofman, Coll. Czechoslovak. Chem. Commun., 13,300 (1948).
593. Smith, J. Chem. Soc., 1953,803.
594. Blaise and Koehler, Bull. Soc.Chim. France, [4], 7,710 (1910).
595. Knoevenagel and Heeren,=, 36,2124 (1903).
596. Huisgen, Seidel, Wallbillich, and Knupper, Tetrahedron, 17, 3 (1962).
- -
382
PART 4
Chemistry of Heterocyclic Compounds, Volume 22 Edited by Richard H. Wiley
Copyright 0 1967 by John Wiley & Sons, Ltd.
The following tables have been assembled into ten groups according to the nature of substituents on the pyrazole ring.
Group 1-Tables 1 to 22: Alkyl- and aryl-substituted pyrazoles.
Group 2-Tables 23 to 38: Carboxypyrazoles and their functional derivatives.
Group 3-Tables 39 to 49: Halogenopyrazoles.
Group &Tables 50 to 55: Nitroso and nitropyrazoles.
Group 5-Tables 56 to 62: Acylpyrazoles and pyrazolecarboxaldehydes.
Group 6-Tables 63 to 69: Aminopyrazoles and their derivatives.
Group 7-Tables 70 to 87: Hydroxy-, mercapto-, selenopyrazoles and
Group 8-Tables 88 to 89: Non-carboxylic acids and their functional
Group %Tables 90 to 94: Diazo, azo, azoxy, oxyazo, thioazo, hydrazino,
Group 10-Tables 95 to 110: Pyrazoles containing more than one r e p r e -
their functional derivatives.
derivatives.
azoamino and metallo-pyrazoles.
sentative function. The nature of t hese functions is indicated in the title of each table.
In each table the pyrazoles are arranged according to an increasing number of carbon atoms in the substituents which, in turn, are o r d e r e d as follows: alkyl, cycloalkyl, arylalkyl, a ry l and heterocyclic. Synthetic methods a r e indicated by roman numerals, sometimes followed by letters. The meaning of these symbols is explained in the following key.
385
Chemistry of Heterocyclic Compounds, Volume 22 Edited by Richard H. Wiley
Copyright 0 1967 by John Wiley & Sons, Ltd.
KEY TO THE PREPARATION METHODS
I a
I b
I c
I d
I e
I f
I g
I h
I i
I j
I1 a
I I b
I1 c
I1 d
I1 di
I1 B I1 f
I11 a
111 b
111 c
I I Id
I V a JYb IVC
From P-diketones, with hydrazine and its derivatives (Ch. 3.1). From acetylenic carbonyl compounds, with hydrazine and i ts derivatives (Ch. 3.11). From a, P-unsaturated, Q -halo, a -alkoxy o r a -amino- carbonyl compounds, with hydrazine and i ts derivatives (Ch. 3. I) . From a, P-unsaturated, P-halo, 0-alkoxy o r p-amino-car- bony1 compounds, with hydrazine and its derivatives (Ch. 3.1). From ethyleneoxides or ethyleneimines carrying an acyl substituent, with hydrazine and i ts derivatives (Ch. 3. X V ) . By conversion of various heterocycles with hydrazine and i ts derivatives (Ch. 3.XIV). From f l -carbonylcarboxylic acid esters, with hydrazine and i ts derivatives (Ch.3.I). From 1, 2,3-tricarbonyl compounds, with hydrazine (Ch.3.IV). From 1,2,3-tricarbonyl compounds, with substituted hydrazines (Ch. 3.IV). From osazones and their derivatives, by dehydration (Ch. 5.VF).
From aliphatic diazo compounds, with acetylene deriva- tives (Ch. 3.VII.A). From vinyldiazomethane and i ts derivatives by internal cyclization (Ch. 3.VII. B). From aliphatic diazo compounds, with halovinyl- and nitro- vinyl-derivatives (Ch. 3.VII. B). From aliphatic diazocompounds, with ketomethylene derivatives (Ch. 3.VII. C). From aliphatic diazocompounds, with malonic derivatives (Ch. 3.VIII. C). From tetrazoles, with acetylene derivatives (Ch. 3.VII.A). From sydnones, with acetylene or ethylene derivatives (Ch. 3.XVI).
By decarboxylation of pyrazole-1 -carboxylic acids (Ch. 5.VII). By decarboxylation of pyrazole -3-carboxylic acids (Ch. 5.VII). By decarboxylation of pyrazole -4-carboxylic acids (Ch. 5.VII). By decarboxylation of pyrazole-5-carboxylic acids (Ch. 5.VII).
By nitrogen alkylation or arylation (Ch, 4. IV). By carbon alkylation (Ch. 4. IV). By alkylation yielding pyrazolium salts (Ch. 4.IV).
387
Chemistry of Heterocyclic Compounds, Volume 22 Edited by Richard H. Wiley
Copyright 0 1967 by John Wiley & Sons, Ltd.
Foreword to the Tables Section
V a
V a1
V b
V b l
V b2
V b3
v c
v c l
v c2
v c3
v c4
v c 5
V c6
v c7
V c 8
V d
V d l
V d2
V d3
V d4
V e
V f
v f l
v g
V h
By substitution of an a ry l or alkyl group with a hydrogen atom (Ch.4.IV). By substitution of an alkyl group with a halogen atom (Ch. 5.111). By substitution of an OH o r SH (OR o r SR) group with a hydrogen atom (Ch.3.XVII;Ch. 5.V-1X.a). By substitution of an SR group with a sulfonyl (SOi)
By substitution of a hydroxy group (or OR o r SR) with a halogen atom (Ch. 5.III-V-IX. C-X. B). By substitution of a hydroxy group with an alkyl o r a ry l - group. By substitution of a halogen atom with hydrogen (Ch. 5. I11 -V) *
By substitution of a halogen atom with a sulfonyl group
By substitution of a halogen atom with a OR o r a SR group (Ch. 5.III-X.B-X.C). By substitution of a halogen atom with a SO,R group
By substitution of a halogen atom with an amino group
By substitution of a halogen atom with a nitro group
By substitution of a halogen atom with a CN, SCN, o r COOH group (Ch. 5.111-VII). By substitution of a halogen atom with an alkyl o r a ry l group (Ch. 5.111). By substitution of a halogen atom with another halogen atom (Ch. 5.111). By substitution of a diazo o r of an azo group with a hydro- gen atom (Ch. 5.VI). By substitution of a diazo o r of an azo group with a nitro- group (Ch. 5.IV-VI). By substitution of a diazo group with a halogen atom
By substitution of a diazo group (diazonium salt) with an azido group (Ch. 5. VI). By substitution of a diazo group with a hydroxyl o r an alkoxyl (Ch. 5. VI) . By substitution of a sulfonyl o r a sulfinyl group with a hydrogen atom (Ch. 5. X). By substitution of a COCl o r RCO group with a hydrogen atom (Ch. 5 . X ) . By substitution of a COOH o r RCO group with halogen atom (Ch. 5.111-VIII). By substitution of a phosphinic group with a hydrogen atom. By substitution of a Hg-X group with a SCN group (Ch. 5.11).
(Ch. 5.X.B-X.E).
(Ch. 5.111-X.E).
(Ch. 5.IJ.I-X.D).
(Ch. 5.III-VI).
(Ch. 5.111-IV).
(Ch. 5.111-VI).
388
Foreword to the Tables Section
V i V ii
VI a
VI 5
VII a
VII b VII c
VIII
lx
X a
X b
x c
X d X e
XIa
X I b
XI1
XI11
XIV a
XIVb
XIVC
By substitution of a nitro group with a halogen atom. By substitution of a nitro group with a hydrogen a tom (Ch. 5.IV).
S y oxidation of pyrazolines and pyrazolidines (Ch. 3 . X ) . By elimination of simple molecules from substi tuted pyrazolines (Ch. 3. XI).
F r o m hydrazonic halides with ketomethylene compounds (Ch. 3.X.A). F r o m hydrazonic halides with enamines (Ch. 3. X. B). F r o m hydrazonic halides with acetylenemagnesium salts (Ch.3.X.C).
Reactions on la teral chains which a r e not descr ibed in this work because considered as general organic react ions.
Decomposition of quaternary pyrazolium sal ts . (Ch.4.IV).
Rearrangement of pyrazolenines and of isopyrazoles (Ch. 3.XII). Rearrangement with dehydration of 4,4-dialkyl-5-hydroxy- pyrazoles. (Ch. 3.XIII). Rearrangement of 3, 5, 5-trisubstituted pyrazolines (Ch. 3. XIII). Rearrangement of dihydro-oxopyridazines. Rearrangement of thiadiazines to mercaptopyrazoles (Ch. 3.V).
F r o m aldehydes arylhydrazones with P-ketoesters in presence of zinc chloride (Ch. 3.VI). F r o m aldehyde arylhydrazones with phenylpropiolic acid (Ch.3.VI).
F r o m diazo-P-diketones o r f rom diazo e s t e r s with keto- methylene compounds (C h. 3. VIII) . F r o m acylphenylhydrazones of P-dicarbonyl compounds with alkaline condensing agents (Ch. 3.111).
F rom aromatic diazo derivatives, with compounds which can undergo coupling at a position p to a carbonyl group (Ch. 3.IX; Ch. 5.V). F r o m diazonium sa l t s and furan o r pyrrole der iva- t ives (Ch. 5.VIII). F r o m P-arylazofurans and pyrroles, with hydroxylamine (Ch. 5.VIII).
389
Foreword to the Tables Section
xv
XVI
XVII a
XVII b
XVIII a
XVIII b
XVIII c
XVIII d
XVIII e
XIX a
XIX b
XIX c XIX d XIX e XIX f XIX g
X X a XX b
XXI a XXIb XXI c XXI d XXI e XXI f
= g
XXI h
XXII a
F rom malonic e s t e r , with arylazides (Ch. 3.VII. C).
F rom halogenocarbonyl compounds with mono - and dithio - carbohydrazides. (Ch. 3.V).
Oxidation of lateral chains to carboxyls (Ch. 5. I; Ch 4.VII). Oxidation of a substituted methylene group to a keto group (Ch.4.1; Ch. 5.VIII).
Rearrangement of an alkyl group f rom a ring nitrogen atom to another (Ch.4.W). Rearrangement of an acyl o r of a carbethoxyl group from a ring nitrogen atom to another (Ch. 5 .X) . Rearrangement of a carbamido group from a ring nitro- gen atom to another (Ch. 5 . X ) . Rearrangement of a nitro group f rom a ring nitrogen atom to a ring carbon atom (Ch. 5.IV). Rearrangement of a nitroso group f rom a ring nitrogen atom to a ring carbon atom (Ch. 5. IV).
Halogenation by halogens, IC1, NaOC1, NaOBr, SO,Cl, and PC1, (Ch. 5.111). Nitration by nitric acid, ni t r ic acid-sulfuric acid mix- tures and nitric acid-acetic anhydride mixtures (Ch. 5. IV). Nitrosation by nitrous vapors (Ch. 5.IV). Coupling with diazonium sa l t s (Ch. 5.IV). Sulfonation and chlorosulfonation (Ch. 5. X. E) . Reactions with S,C1, and SC1,. Mercuration reactions (Ch. 5.11).
Halogenation of aminopyrazoles. Halogenation of pyrazoleselenones o r of pyrazoledisele - nides (Ch. 5. X. F).
Oxidation of the nitroso group (Ch. 5.IV). Oxidation of the hydroxylamino group to nitroso group. Oxidation of the hydroxylamino group to azoxy group. Oxidation of an amino group (Ch. 5.V). Oxidation of a hydrazo group (Ch. 5.V). Oxidation of a -SH (or SeH) group to S-S(or Se-Se)
Oxidation of a -SR (or SeR) group to SO,R (or Se0,R)
Oxidation of a -SH (or SeH o r SeR) group to SO,H (or Se0,H) (Ch. 5.X.E-X. F).
F rom nitrosopyrazoles, with compounds containing active methylene groups (Ch. 5. IV-VI).
(Ch. 5.X.C-X. F).
(Ch. 5.X.B-X.D-X. F).
390
Foreword to the Tables Section
X W a1
XXII b
XXIII a XXIII b XXIII b l XXIII c XXIII c l
X W I d XXIII e XXIII f XXIII g XXIIIh
XXIV a X X N b
XXVa
XXVb
xxv c
XXV d
XXVe
XXV e l
XXV e2
xxv f
XXVI a
XXVI b XXVI b l XXVI c
XXVI d
F r o m aminopyrazoles, with aldehydes or ketones (Ch. 5.VI). F r o m aminopyrazoles with nitrosopyrazoles (Ch. 5. IV-V) . Reduction of NO, to NO (Ch. 5. IV). Reduction of NO, or NO to NH, (Ch. 5.IV-VI). Reduction of NO, or NO to an azo group (Ch. 5.IV). Reduction of an azo group to an amino group (Ch. 5.V-VI). Reduction of an azo group to an amino group followed by semidinic rearrangement (Ch. 5. VI). Reduction of an azo group to a hydrazo group (Ch. 5.V). Reduction of -SO- or of -SO,- to -S-. Reduction of a -S-S- group to a thiol group Reduction of a -COC1 ProuI) to -CHO (Ch. 5.VIII). Reduction of a -S02ClY(or ̂ SO,R) group to -SO,H (Ch. 5. x-XI).
Hydrolysis of a -CC1, group (Ch. 5.VII). Hydrolysis of a -dihalogenated alkyl groups (Ch. 5. VIII).
Nitrogen acylation of magnesium or lithium pyrazoles with chlorocarbonates. Reaction of magnesium or lithium pyrazoles with car- bon dioxide (Ch. 5.11-VII). Reaction of magnesium or lithium pyrazoles with acyla- ting agents (Ch. 5.11). Acylation at positions 1 or 5 by sulfonic, sulfinic or sul- fenic halides. (Ch. 5 . X ) . Acylation at positions 1 or 4 by acid halides or anhydrides
Nitrogen acylation by acyldiazomethane, followed by heat- ing or U.V. irradiation (Ch. 5. XI). Formylation a t position 4 with a dialkylformamide and phosphorus oxychloride (Ch. 5. VIII). Nitrogen acylation by chlorocarbonates and isocyanic acid e s t e r s (Ch. 5.VII). F r o m pyrazole -3 -carboxylic acids, on treatment with acid halides (Ch. 5.VII).
(Ch. 5. VIII-IX. B-XI-X. D).
By alkylation o r acylation of pyrazolones, pyrazolethiones or selenopyrazoles (Ch. 5.VIII-1X.A-IX. B-IX. C-X.A-
By alkylation or acylation of aminogroups (Ch. 5.VI). By alkylation of pyrazolonearylhydrazones. Rearrangement of an acyl group from nitrogen to oxygen in N-acyl-pyrazolones (Ch. 5.IX. B). Rearrangement of an alkyl group from nuclear nitrogen to sulphur, selenium or to non-nuclear nitrogen in N - alkyl-pyrazolethiones, selenopyrazolones o r aminopyra- zoles (Ch. 5. VI-X. B).
X. B-X. F).
391
Foreword to the Tables Section
XXVI e XXVI e l
XXVI f
XXV1l a
XXVII b XXVII d
XXVII e
XXVII h
XXVIII
Alkylation of -SO,H groups to -SO,R (Ch. 5.X. D). Pyrazole ketones from acid chlorides o r from es te rs of pyrazolecarboxylic acids (Ch. 5. VIII). From pyrazolones or from aminopyrazoles, with isocyanic, isothiocyanic es te rs or with carbon disulfide
From nitrosopyrazoles with alkalies (Ch. 5. IV). From pyrazolediazonium salts with alkalies (Ch. 5.VI). By hydrolysis of groups joined to amino nitrogen (Ch. 5.VI). From pyrazolecarboxylic es te rs o r amides with hydroxy- lamine. From diazopyrazoles, with mineral acids (Ch. 5. VI).
From Q -dicarbonyl compounds with hydrazinoacetic acid derivatives (Ch. 3.111. B).
Literature references relate to synthetic methods indicated on the
Among derivatives a re reported functional derivatives and salts.
same line. Boiling and melting points a r e in centigrade degrees.
392
0 c k a, 8 :
W 0 Ln
r( r(
N
C - W H 0 0 O O N 0 0 N m m v) Ln
0 0 Ln
2 I 3 m m
cd
2
m 03 -$
cd
2
m
393
TA
BL
E 1.
1 -A
lkyl
- or
Ary
l-su
bst
itu
ted
Py
razo
les
TA
BL
E 1
(co
ntd
)
G)
W *
Met
hod
s N
. R
of
sy
nth
esis
M
.p.o
r I3
.p.
Ref
eren
ces
Der
ivat
ives
6 7 8 9 10
11
CH
2CH
3
CH
2CH
0
CH
2CH
2NH
2
CH
2CH
2NH
CH
,
CH
2CO
OH
12
CH
2CH
2CH
3
13
CH
,CO
CO
OH
Ia
B
. 13
6-13
7"/7
47
25
IV a
B
. 66-
70"/
0.7
986
VII
I
VII
I
VII
I
IV a
VII
I
Ia
VII
I
519
519
519
M. 1
64-1
66"
51
9
519
B.
166-
167'
,"75
5 25
974
Pic
rate
: M
. 135
-136
"
Die
thyl
acet
al: B
. 11
2-11
9"/2
3
2,4
-din
itro
ph
enyl
hyd
razo
ne
M. 1
73-1
73.5
"
'2H
C1:
M.
120-
130"
Dip
icra
te: M
. 176
-178
"
.2H
C1:
M. 1
20-1
30"
Dip
icra
te : M
. 162
-164
"
'2H
C1:
M.
130-
140"
Dip
icra
te : M
. 17
5-17
7"
Eth
yl e
ste
r: B
. 13
0°/2
0
Am
ide:
M. 1
51-1
53"
Met
hyl
amid
e: M
. 11
0-11
1"
Dim
eth
ylam
ide:
M.
112-
113"
Pic
rate
: M
. 99-
100"
Eth
yl e
ste
r: M
. 74
-75"
W
W
UI
,CO
OH
14
-C
H,--
CH
N
atu
re
IV a
(?
)
VII
I
WH
,
15
CH
,CH
,CH
,CH
, I
a
I11
c c, d
Vb
f
VIa
b
M. 2
36-2
38"(
d)
395,
792
39
5,7
92
M. 2
43-2
44"(
d)
986
B.
174-
175"
/745
25
.
B. 8
1-82
"/3
0
863
5
B. 2
55-2
57"/
750
515
B.
134-
135"
/15
M. 2
02-2
02.5
"
507
507
B.
246-
247"
38
1
B.
107"
/7
267
B. 7
4"
/0.0
5
48
9,1
00
9
572
266
977
74
44
0
31
,84
8
Ace
tyl
der
iv. :
M.
153-
153.
5"
Nit
rile
Pic
rate
: M
. 77-
78"
Dim
eth
yl e
ster
: M
. 13
9"
M.
158"
-AuC
13
HC
1: F
. 1
80
.5-1
81
.5"
-14P
tC1,
.HC
l . l
,$Pt
C1,
. l
,$H
,O
m W 0 r3
Ln
\
N w 3
I W m 3
0
0
a
cd CI
m X 0
?j 0 cy
m W 0 3
Ln
\
0 0 4 3 I
0
k a m * 2 scd
cd CI
.-I + 3 cu
4 N 0 0 3 m m
m m I
W W
2
4 0 w w m e ¶
Ln m I
4 m
Ln
s
N
2
3 3 W W m
0 N c- 3
0 0 I w o 3 w c - f - 3 3 3
s s s
Q N N
m N x
2 I
Q
Ia
M
. 41"
10
83
c1
B.
118-
120"
/2
Ia
M
. 10
7-10
9"
38
1,1
07
9,1
13
1,1
13
2
d M
. 10
9-11
0"
85
0
B. 2
46
,5"
/75
4.1
10
6 28
5
**
M.
32
,5-3
3"
10
6
29
ec
n3
**
VIB
B
. 258
-259
"/75
6.9
380
Ia
M
. 13
8-13
9"
28
VII
I M
. 14
0-14
2"
28
,10
7
31
-@
eon
VII
I M
. 26
4-26
5"
107
32
VII
I M
. 11
6-11
7"
382
4
W
w
33 QQ
c1-
1
13
3
.HC
llg
PtC
l, : M
. 2O
O-2
0lo(
dec.
)
.HC
1 . l
hPtC
1, : M
. 18
3-18
4"(d
ec.)
Hy
dra
zid
e : M
. 13
5-13
7"
Eth
yl
est
er:
B.
308-
310"
Eth
yl
est
er:
M.
61-6
2"
~H
~C
H~
OH
* F
rom
ep
ich
loro
hy
dri
n w
ith
ph
eny
lhy
dra
zin
e **
Fro
m e
pic
hlo
roh
yd
rin
wit
h 0- o
r p-
toly
lhy
dra
zin
e
T-4
BL
E 2
. 3(
or 5
)-A
lkyl
- or
Ary
l-su
bst
itu
ted
Py
razo
les
H
CD
m
w
H aq'
I B M
eth
ods
Ref
eren
ces
Der
ivat
ives
N
. R
of
sy
nth
esis
M
.p. o
r B
.p.
1 C
H,
Ia
b
c d
I1 a
b
I a-
I11
a
2 C
H,C
1
I11
b
C
Va
VIa
b
* VII
I
M. 3
6-37
"
23
8,3
97
,54
7,5
48
,78
7,7
88
B. 2
04"
/7 5
2 8
92
,89
4,1
08
8,1
14
0
B. 2
00"/
748
1017
,101
9
B.
108"
/25
1016
,101
9
25
,57
7,
787
862
296
1018
,101
9,10
25
58
,30
0,3
01
,62
7,6
29
829
247,
248
439
1019
351
M.
155-
156"
51
5,11
35
.AgN
O, : M
. 121
"
'3H
gClZ
: M.
165-
168"
.PtC
1, :
M. 2
53"
.2H
C1.
PtC
1,
.2H
z0
: M
. 18
1"
Ag
salt
Pic
rate
: M
. 142
-145
"
Pic
ryls
vlfo
nat
e: M
. 216
-217
.5"
-(C
l--@
0,)2
. NH: M.
13
4-3
5'
3 C
H,O
H
4 C
HZ
OC
H,
5 C
H,N
H,
6 C
HZ
CH
,
7 C
XC
H
8 C
HzC
HO
9 C
HZ
CO
OH
Ib
I1 a
VII
I
I1 a
VII
I
Id
VIa
V
III
I1 a
If
VII
I
B. 1
37-1
40"
/0.5
B. 70" /o
. 1
B. 1
07-1
08"
/15
B. 9
0"/1
2
M. 4
5-46
"
B. 8
6"/4
M. 10
7-10
9"
B.1
06
"/0
.4
518
515,
1136
515,
1135
862
583
25,3
87
297
29 7
297
518,
1142
515,
518,
1135
10
CH
ZC
HZ
NH
, VIII
B. 1
20-1
30"
/0.5
51
5,51
8
B.1
18
-12
3"
/0.5
w
W
(D
*"F
rom
3-m
eth
ylen
pyr
azol
ine,
dro
ppin
g it
on
a m
ixtu
re o
f K
OH
, Ag,
Pt,
hea
ted
at
200"
'HC
1: M. 1
17-1
18"
Pic
rate
: M. 1
81-1
82";
184
-185
"
Pic
rate
: M
44"
Pic
rate
: M
. 127
,5-1
28"
; 12
9"
Pic
rate
: M
. 122
-124
"; 1
26-1
27,5
"
Hyd
razo
ne:
M. 1
22-1
23"
+HC
1: M. 1
16-1
17"
; 13
7-14
0"
Eth
yl e
ster
: B. 1
06" /
O. 4
Eth
yl e
ster
.HC
I: M
. 107
-109
"
Am
ide:
M. 1
48-1
49"
Nit
rile
: B
. 117
-120
"/0
.4
Nit
rile
-Pic
rate
: M
. 63-
64"
.2H
C1:
M. 2
24-2
27"
Dip
icra
te : M
. 195
-197
"
h
B 0 v
N
w ;1 m 2
w 3
3 0 1 w N 3 3 N 3
W 3
Ln
i?
\
0 m N
I 0 C Y N
0
a
3 3
w L n 3 1 - w 3 3
m 3
3
a,
k u
E
00- Ln
C - N Z G
m 0 w
0 w d
ri 1 3 I
2 3 ... Ln
cd 0 3
Ln I
2
0 CO W 0
I 3
w ?+ C- W
a, a, d 0
* * 2 )i: 6
d P CI
mm : : u
N 3
t- 3
W 2 , " 4 n ?+
400
m w I
w
3 W I 0 W
I m In
03 ln
I
m t-
I w m
I
0 w W
2 3 W
s t- m
rj 2 0" z, ..
c 2
W
f 3
0 0 m 3 I
3
f- W 3
I h N 3
zi
mm u 2
2 mN
h
u
u v
h
2 2 u
u v
h . N m u
u
v
2
m w N N
3 N N N
m o 3 N
m 3
f- N
m W N N
40 1
q v 8
W !J m
p: 2 I 2
N m 3 W W m
m m I
Fu m
s
3 m m mi N
W co W
W
3 3
In 3
I In
L- Q,
o In 3
i
a 0 3 CII m m m ca
402
33
-CH
,(C
H,)
,CH
, M. 88. 5-89.5"
862
34
C,H
, I
a
M. 72-74"
b M. 78-79"
C
B. 310-315"
d
B.
200"
/20
f B. 177-178"/11
I1 a
1 a-111 a
I11 b C
b, c
11
1 c-
V
a
VIa
Vb
V f
-VI
a
WIa
VII
I
Id
M. 89-90"
Pic
rate
: M. 169"
213,550,552,558
Ag s
alt
: M. 85"
192
342
.HC
1: M. 144-145"
542,581
541
535
Pic
rate
: M. 16
8-171"; 177-178"
121
216,550,955
308
212,552
463
.HN
O, : M. 126"(dec.)
.HC
1 .
lhP
tC1,
. H
,O:
Dec
. 193" M
. 218"
162
454
213,439
21
581
Id
M. 98"
581
TA
BL
E 2
(co
ntd
)
rp 0
rp
Met
hod
s N
. R
of
sy
nth
esis
M
.p. or
B.p
. R
efer
ence
s D
eriv
ativ
es
38
39
*C
H.
40
~O
CH
~C
H~
CH
~
41 O
OC
~H
~
42
G
4
3
4=&02
Id
M
. 127
"
Ia
M
. 98-
99"
VIa
M
. 126
"
Ia
M
. 80"
b
I11
b
VIa
B
. 256
"/11
Id
M
. 120
"
Id
M
. 19
2-19
3"
Vf
il
VII
I
581
1077
,110
3,11
04
452
846
846
846
452
581
581
310
310
21
3,3
10
,55
3,7
69
'HC
1: M
. 158
-164
"
Pic
rate
, M.
127-
128"
*H
N0
3: D
~c
. 182-
184"
M.
128"
4 N
0 In N I-4
s
u Y
0,
rD t-
m- 3 N
N 4 > 0 0 m
r" z I
p \ Q Q w In d. w
cc) I-4
N
Y l-,
ji
(0 W
I-4 N
0 m W 3
z;
Y
s"
I z, m
f- w
w
3 2 t- t- 0 I-4
& In 3
t- v) 3
I
s
ol Y
m
P-
2 4
t- 0 3
0 N ua 3 I 0 In 3
s
cd U
0 In
03 Q, v W
405
m Q, 3
,i W cd U
*
ii:
N m *
0 3
b 0 Q, 3
I co 03 i
a
N
s
" X
% Y
8
2 "
m
&I 0
4 d
s
ea m w
3 3 >
a
m W 3
cd
F
N - E" u I X V
l-4 N m m
0 c- c- N
si:
1 s
.. W Y
0
m m m m
rl i
w w w w * m m 3
0 m
I
m i
3
In 3
2
m W m m w In W m m
406
TA
BL
E 3
. Q-Alkyl- or
Ary
l-su
bst
itu
ted
Py
razo
les
N.
R
Met
hod
s of
syn
thes
is
M.p
.or
B.p
. R
efer
ence
s D
eriv
ativ
es
1 C
H,
2 C
H2C
1
3 C
H20
H
Ia
d
111
b
I11
b,d
-VII
I
VIb
VII
I
I1 a
Va
VII
I
Ia
d
111
b
M. 1
5.8
-18
.5"
84
7,10
65
AgN
O, : M
. 142
"
B. 2
04-2
05"
20
2 P
icra
te : M
. 142
"
B.
107-
109"
/16
515,
793,
828
B.
95"/
13
278
B.
70-7
3"/3
84
1
515
M. 1
26-1
27"
51
5
515
515
B.
122"
/16
847
B. 1
04-1
05"
/3
202
B. 8
2-85
"/3
25
Pic
rate
: M
. 14
9-15
Oo(
d.)
Pic
rate
M. 1
30-1
35";
137
"
0 0 m rl
I Q) cu rl
z4 G x ..
co rl m
z s
2 x
x u
m
co rl m
0 m m I * m
A
W U
3:
3:
x V
ON
W
0 co cu cu
I
0 W rl rl I
m rl rl
2 .. G T
P c o m * A cu c o r n
U
" F f: U U U
408
0 m 0 rl I
w 5: ri G ?
..
C O W r l r l m m
0 0 0 0 m m m rl rl rl
m m r ( r l m r l rl rl rl
c- 0 L n
rl m
e, 0
m 0
0 \
$ $ % ! g
I W m rl
A
rl N N
ri r i i
0
3 0
3 w rn
N
ti- N - n
X X ON X u, % X u
3 N
40 9
TA
BL
E 3
(co
ntd
)
Met
hod
s of
N
. R
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
22
C,H
, I
a
M.
230-
231"
f
I1 a
I11 by
d
b
I11
by d
-VI
a
Vd
VIa
b
847,
906
Ag
salt
54 1
-H
Cl:
M.
215-
218"
535
209,
210,
215
Pic
rate
: M
. 15
5"
554,
829
210,
219,
221
816
210,
220
93
*HC1: 1
/2P
tCI,
: M
. 287
"(d
.)
1 1
m .b c)
.f 4 B P
co m 3
!n
a
9
411
& m I m I-
I 0
2 N In 3
5: i
2 4 &
3
a,
0
3
m m
N 3 3 In m - 8 0 2 m
m m m a Q)
m m m m m 0 4 m r n
m 0
2 I- * a
d i V
d V
W
n
N m m 2 3 3 3
* * 3 m
TA
BL
E 4
. (co
nt.)
N.
R
R’
Met
hod
s of
sy
nth
esis
M
.p.
or B
.p.
Ref
eren
ces
Der
iva
tiv
es
t- L- 3
W L- ?-I
I
rn oo
m
il
a,
il
Y Y
ii: ii
I
413
p:
3 m
0 m Q1 nr r m I i l x N N
z? u N m
414
3 ..
415
m 4 1
w w w w w w w w E - m w * * w * * * w ca m m m c o w m c o m c o m 3
E- 3 3
I W 3 3
J
s * 3
i
s 4 3
9 c) N 3
i
& 0 4
I m 2 i
b 3 3
z-
m
m' m
i & m
J
m UY 3
m UY 3
i
B V
N L n
416
3
3 W
b m 3
2
3
Y X'
0 d
b m 3
I 00 n 3
i 5: .- a, 5
x 3 c
s
- Y 5
n N k
i
c- in 3
d Y
3 W
417
I J
i 3
L- m * n m (D
8 m *
c' c) 3
m N N
* 01 N
I
i i
d d CI 3
* (D m W
N m N 0 0 3
N 0
2
m c) rl
i N (D 3
i
L m I
d
m m 3
i
rd d rd d
3 H 3 : s
G V
m W
2 Ern v v
v) W * W
3
t- (D 3
cd
418
8 i i
f
n
0-
m- m
m-
N i i
0 i *
t-
N
H m L-
N t - n t- t-
w n" m t -
n m
m- "
L-
w N m w
N m
L- m
M
m i
z!
k cr i
z!
'CI CI
w ci
id ci
2 V
i L-
m X V
2 V
m L- m t- cr t- W t- L- t- N L-
419
m 3 In
F
In 0 i
i
m m
N m
3 m
0 m w In
m m
420
b In
L 0 N
i W Y
2 ir,
" E- m
m 2
8
Y
c .3
4
* R
a s
m E- m
m N 3
b m & 3 m 3
i i m
w 7 n
E 64 E
0-v)
2" I
0 m
* E- E-
N o w d m
& Ln 3
m m 8 8
* Q, m m m m
42 1
TABLE 4
. (co
nt.
)
Met
hod
s of
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
N
. R
R
' * N
N
yC
H3
-C
H=
CH
al
n
ow
96
It
I
1
If
M
.154
-155
"
774
H
&H
I
C6
H5
I
97
<H,C
--C
H=C
HC
,H,
C,H
, I I OH
98
C,H
,
99
C,H
,
100
C,H
,
C6
H5
Ie
Ia
b
C d
I a-
III
a
I c-
I11
a
I d-
IX
a
VIa
b
VI
a-V
f
*
M. 1
78-1
81"
60
8
M. 1
99-2
00"
1
1,3
40
,61
0,5
67
,90
2,1
04
4
.HC
1: M
. 232
-233
"
M .2
04
"
746,
747
Pic
rate
: M
. 161
-163
"
B. 3
47"/
155
2, 3
42
Com
poun
d w
ith
1,3
,5-
B. 3
17"
/160
3
3,3
4,7
3,5
67
,90
2,1
04
4
trin
itro
ben
zen
e:
84
5,9
02
,10
44
M
. 135
.5"
342.
866
2,8
45
,90
2,1
04
4
439
1036
,103
7
454
406
Ia
M. 1
44"
10
4
Ia
M
. 159
-160
"
523
b
M. 1
63"
746,
747
VI
b
40
6,5
23
w OI
m 0 m m
W L!am m c n 2 2 % El 2 3
cn Ln
L!Y
3
El
i n n in =: :- u =a =a u v
423
w m w c u w m
b K
$ 8 i i
w m a 3
N 3
r d r d w w
0 3 N N 0,
3 3 3 3
m 3 3
r 3 3
m + 2 2 s N
i l z 3 3 3 3
8 m
rd CI
Q
N N 3
424
t - t - t - t - P t -
n w 3
s
d w CI
t - t - c - t - t - t - t - t - t - t - t - t -
In N N
I w N N
& 0 N
I m m 3
s s
r d w d w
ar” CI
In 3 m
w m 3
s E’ rd d
7 ! CI CI
E
n N 3
w N -
?YS ‘4
s In N 3
y. u=u
I =
(D N 3
t- N 3
TA
BL
E 5
. 3,
4-A
lkyl
- or
Ary
l- D
isu
bst
itu
ted
Py
razo
les
N.
R
R' M
eth
ods
of
syn
thes
is
M.p
. o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
1
CH
, C
H3
Ia
ma
2 C
H,
CH
,CH
,CH
, II
c
4 C
H,
C6
H.5
I
a
III
b
VI
b
VII
I
5 C
H,
6 C
H,
-(-J
If
M. 5
5-58
'' 2
5,7
4,3
33
,79
3,1
06
5
Pic
rate
: M
. 153
"
B. 1
11"/
10-1
1 10
25
B. 1
21'Y
lO
817
.HC
I: M
. 17
1"
Pic
rate
: M
. 104
"
B. 1
02-1
03"/
11
50
M. 1
40-1
41"
1
7
Pic
rate
: M
. 15
5"; 1
58-1
59"
0.0
05
817
737,
817
17
M. 1
20-1
21"
1
5,1
8,1
9,2
0
.2H
C1:
M. 2
50-2
52"
.HzS
O,:
M
. 266
-268
"
Pic
rate
: M
. 19
1-19
2"
cu m rl
N 0 3
I
s
P- 3
m cu 3 I
-F cu rl
>
a
In rl
d E I * U P W
0 m 3
W : F U
3 cu 3 rl
0 rl
m -F rl 3
L n 3
427
h
Y c 0 V Y
m' w d m 2
m 9* m
a m m l-l
N m d
I
N h m
z = O Y I'
I
W rl
m -# m
d
I
0" z N n m
co rl
W d
w H
N h
x" V 3: CI
3 u
0 N
I m L- d
m W -#
5 W
m
zi
d Y
z - V
rl N
42 8
m 0 N
w 0
P
El
m 5: V
0 m rl
W 4
rl W rl
0 Ln Ln rl
I w m rl
I
i r’
LD
% V
z? U
V In @ g V
N N
-3 N
m N
% 3
m I
c*) m 4
r’
4 V
m N
W N
I
42 9
TA
BL
E 5
.kon
t.I
* 0
w
Met
hod
s of
N
. R
R
' sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
32
-CH
2CH
2CH
2-
Ia
IIIa
b
3 3
-CH
,CH
2C
H(C
H ,)-
IIIa
36
XH
ZC
H2C
H2C
H2-
I
a
IIIa
M. 1
27-1
27.5
"
M. 1
45-1
46.5
"
M. 5
7-59
"
Oil
Oil
M. 8
9-90
"
M. 8
4"
B.
151"
/14
498
502
9 'H
Ck
M. 2
03.5
-204
.5"
1025
P
icra
te:
M. 2
38.5
"
86
1025
.H
C1.
P
t C1,
1025
.H
C1.
'h
P
tC1,
1025
'H
C1.
1/2
PtC
1,:
M. 2
20-2
22"
1025
9,10
65
Ag
sa
lt
1025
.H
C1
IV a
vm
c1
37
)C(O
H)C
(OH
)2C
C1=
CC
1-
VII
I
38
XH
,CH
(CH
,)C
H~C
H~-
I
a
ma
39
-CH
,CH
,CH
(CH
,)CH
,- II
Ia
40
-CH
,CH
(CH
,)CH
,CH
(CH
,)-
I a
-m a
m
a
/CH
3 41
-CH
(CH
S)C
H~C
H~C
H-C
m
'
pC
H2
42
XH
(CH
~)C
H~
CH
~C
H~
- I
a
I a-
III
a
(cH
,),=c
H
W *
43
>CH
CH
,CH
,CH
(CH
~)-
III
a
44
XH
(CH
,)CH
,CH
,CH
'' 11
1 a
c..
CH
(CH
3),
\
446
409,1151
M. 155-160°(d)
408
M. 99-100"
1025
1025
M. 74
-75.
5"
89
B. 168"/20
M. 76-77"
89
B. 151-152"/10
89
Oil
1025
B. 152.8"/12
57
57
Oil
Oil
1025
1025
.HC
1. '1,
Pt C
1,
.Pic
rate
: M
. 155-156"
.l/2A
gNO
,: M. 137-139"
Pic
rate
: M
. 136-138"
.HC1
Pic
rate
: M
. 156-157"
Pic
rate
: M
. 167-168"
.HC
1. l/Z
P
t C1,:
M. 201"
Ag
sal
t
.l/Z
AgN
O,:
M. 132"
.HC
1
Pic
rate
: M. 151-152"
.HC
1. 1/
2 PtC
1,:
M. 216"
.HC
1. '/2
PtC14: M
. 226-228"
TA
BL
E 5
. (co
nt.)
N.
R
45
46
47
48
Met
ho
ds
of
R'
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s ._
- -
~ - -
~~
__
__
~_
__
~
__
D
eriv
ativ
es
- %"'..$ H-
C(C
H
I - (
C€1
3)-
CH
zCH
2-
Q
1025
.HC
1. '12
Pt C
l,:
M. 188-190"
I a-
III
a O
il
III
a M
. 149-150"
1025
.HC
1. 1/2 P
t C1,
Ia
I a-
III
a
Ia
IIIa
Ia
Ia
M. 135"
9
M. 123"
96
B. 212-213"/11
Pic
rate
: M
. 102-1 93.
M. 66-67"
223,224,1003
.HN
O,: M. 144"(d)
1025
.HC
1. 1/2 P
t Cl,:
M
. 238-239"
M. 106.5-
1003
10
7.5
"
M. 114-115"
224,1003
B. 149-151"/
0.01
3,4
-Ste
roid
o-P
yra
zole
s
Met
hods
of
R""'
, sy
nth
esis
M
. p.o
r B
.p.
Ref
eren
ces
Der
ivat
ives
R
t R
" R
"'
R"
1H
H
H
OH
H
H
Ia
M
. 248
-251
.5"
275
a
2 H
H
H
O
H
CH
,CH
, H
I
a
M.
149.
5-15
0.4"
27
5 a
3H
H
H
OH
H
CH
, I
a
275
a
.C,H
,OH
. M
. 1
27
.6-1
28
.47
21
7-22
5"
4 H
H
H
O
H
CH
, C
H,
Ia
M
. 22
9.8-
242"
27
5 a
N-a
cety
l de
riv.
: .C
,H;O
H:
M. 11
1.4-
115.
4"
N-p
ropi
onyl
der
iv.:
M
. 13
4.4-
14
8"
N-(4-chlorphenoxyacetyl) de
riv.
: M. 1
64.8
-167
.6"
5 H
H
H
O
H
CH
ZC
H,
CH
, I
a
275
a .C
,H,O
H:
Sy
nte
r. 1
40-1
50";
M
. 249
-51"
* W
w
6 H
H
H
O
H
C-C
H
CH
, I
a
M. 2
37.4
-242
" 27
5 a
7 H
H
H
O
H
CH
,CH
,CH
3 C
H,
Ia
M
. 217
.6-2
20.8
" 27
5 a
TA
BL
E 5
. 3
,4-S
tero
ido
-Py
razo
les
(con
t.)
__
-~
_
__
__
-
Met
hods
of
R""
' sy
nth
esis
M
.p.
or
B.p
. R
efer
ence
s D
criv
ativ
es
* N.
R'
R"
R"#
R'"
w
rp
~_
__
__
_
._
8 H
H
H
O
H
C-C
CH
3 C
H,
Ia
D
ec. -143"
275
a
9 H
H
C
H,
OH
C
H,
CH
, I
a
M. 156-174"(d)
275
a
10
CH
, C
H,
H
OH
C
H,
CH
, I
a
M. 269.2-274.6"
275
a
Met
ho
ds
of
N.
R
R'
R"
R"'
sy
nth
esis
M
.p.o
r B
.p.
Ref
eren
ces
Der
ivat
ives
1 O
H
H
H
H
Ia
M
. 272-276.6"
275
a
N, 0
-dip
rop
ion
yl
deri
v.:
M. 107.6-112.6"
2 O
H
CH
,CH
, H
H
I
a
M. 284.4-290.6"
275
a
3 O
H
CH
=CH
, H
H
I
a
M. 247-259.4"
275
a
4 O
H
C=
CH
H
H
I
a
M. 239.6-246.2" 275
a
5 O
H
CH
,CH
=C
H,H
H
l
a
M. 239.8-248.2"
275
a
6 O
H
H
OH
H
I
a
M. 233.2-246"
275
a N
, O(R
)-D
ipro
pion
yl d
eriv
.: M
. 107.6-112.8"
7 O
H
CH
, 4-
Ia
M
. 233.2-246.8"
275
a
Met
hods
of
N.
R
R'
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
1 O
H
H
Ia
M
. 231
-233
.6"
275
a
2 O
CH
, H
I
a
M. 2
36.4
-239
.2'
275
a
3 O
H
CH
, I
a
M. 2
70.4
-276
" 27
5 a
~-
~
Met
hods
of
N.
R
R'
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
1 O
H
H
Ia
M
. 272
.8-2
77"
275
a A
w
U
l
2 O
H
CH
,CH
, I
a
M. 3
05-3
15"
275
a
rl
D? u
L-
L?
0 @a w rl I
rl * rl
i
W f-
5: 5:
n B v) rl
W r3
i i
P Q
2 2
I
m
u D? u
N m
436
I!-
I:
I: I
W
4 p* rl I c) p* 3
z!
0 W d. 3 I
N p* 3
i .. a U cd k
iz
a, +.'
ii: k
.. a, c, d
V
ii: E; ?
Q, r(
0 3
CO- 3 0 3
c- 0 ln
0 Ln cu
W
5 Ln
3 r(
W 3 I-I
I
a
Ln c- 3
0 3
W r3
W W cu
z! ai m P
in
u m
u G u 2 u 2 u
/ I x Y-0 in
2 u I I m
In =W
=W u kz u 3 u
2 3 u
2 3 u 2 u 2 u
r( Q) 5 r(
437
m W c- W
& Q) I t- Q)
s .. a, Y cd
V
ii
w- w i w- + r w m t - O N N N Q )
3- In- w- t-- m m - t - w N m m 3
m N N N m W
2 2 od m
N 3 I
m
N 3 c-'
a
V
P V d ,
3 8 v n a
m N w
m > 2 3 I
3 t- 3
m'
El 3
2 u
< u
N 3
m N *
El 3
W w m
3 W 3
s
P
El
w 0 m W x 3 N
m 0
2 k 3 3
m 3
m ' d
El 7 w rd
Y U
El 3
P I
% u k7 u - Q (D t- w 3 3 3
v c- N
0 f- c-
- 3 3
N 0 c3
0 N
I u3 3
i% m l-l
a i a i
d d U U
d U
n =a V V
It m V
n
=a V
N N
El P
2" 4 j n =W u
n 0
xW V
?.a V
n n =W V
=W V
v N
W cu u3
N l-l N
0 N
43 9
m W m
co rl m
i
P
fi
Y)
=a + n
=&I
u
0 m
In c- c-
h -8 I
N w
i
P
fi
?TJ e
n
5 u
N m
co W n
0 rl t-
2
P
fi
0 8 10 =.
u
m n
In m N
b W N I 0 c- N
n
0
d ii
Ern u
x"
Q w m
0 t- t-
a a * d
44 1
TABLE I. 1, 3 ( o r 5)-Alkyl- o r Aryl -d isubs t i tu ted P y r a z o l e s (with unass igned s t r u c t u r e )
~~ ~~
Methods of N. R R' s y n t h e s i s M.p. o r B.p. R e f e r e n c e s D e r i v a t i v e s
1 CH,OH CH3 IV a M. 79" 500
IV a M. 183" 5 6
H?C B r
3 - CHZ +OH CH, IV a M. 206' 56
CH3 B r
C 6 H 5 CH,CH,COOH 111 b o r d M. 120" 1049 Ag salt
B. 235"/20
CH2CH(OCH3), VI a M. 94.5" 343 &NO2
CH(CH,), I a 249
C6H5
C6H5 -+ I a M. 127" 146
C 6 H 5 M. 90-91" 150
442
m 0 3
c W 3
I
i
4 :: f
0 * 3 3
3 1 1
443
I I
3 3
3 0
I (D 0
- 3
m
m 0
m 3 - 3 - 3 3
* l n D ( D t - o m 3
444
20
CH
,CH
,NH
, C
6H
5
21
CH
,CH
,N(C
H,)
, C
6H
5
VII
I
Na
519
B. 133-135"/1
205,519
B. 125-128"/1
205
.2H
C1:
M. 1
82-1
85"
.HC
I: M. 135-136"
.2H
C1:
M. 18
5-187"
B. 1
68
-17
1"/
1
519
.HC
k M
. 216
-218
'
VII
I M. 63
-64"
519
B. 200-202°/1
.HC
1: M
. 198-200"
23
CH
,CH
,NH
CH
2C6H
,
24
CH
,CH
=CH
, C
H3
111
d
Na
M
B. 171"
51
51
51,65
Pic
rate
: M
. 77.5-18.5"
25
CH
2C,H
, C
H3
Id
Illd
IV a
VII
I
B. 141.5"/15
55,72
B. 13
7"/10
72
55,72
519
Pic
rate
: M
. 114"
.HC
L M. -105"(d)
26
CH
,C,H
,
27
CH
,C,H
,
CH
,C1
CH
,OH
V
IU
B. 150-153"/ 12
519
28
CH
,C6H
,
29
CH
,C,H
,
CH
,OC
,H,
CH
,CO
OH
VIU
VII
I
B. 160-165°/15
519
M. 125-127"
519
Eth
yl e
ster
82%:
B. 158"/12
Met
hyl
amid
e 90%:
M. 70
-71"
Nit
rile
30
CH
,C,H
,
.a
Ir
01
31
CH
,C,H
,
CH
,CH
,NH
, V
III
CH
,CH
,NH
CH
, V
Ill
519
519
.2H
C1:
M. 183-185"
Dip
icra
te: M. 136-138"
.2H
C1:
M. 146-148"
TA
BL
E 8
. (co
nt)
. ~
P
a
0)
N.
R
32
CH
,C,H
,
38
CsH
5
39
CsH
5
R'
CH
,OH
CC
l,
~~
-_
M
eth
ods
of
syn
thes
is
M p
or
B p
R
efer
ence
s _~
_
__
~~
-
--
-
-
IIf
M. 5
8-60
" 48
9
VI
a 46
3
VI
a M
.11
8-1
18
.8"
97
0
VI
a-IV
a
589
IV a-VI
a 58
9
IV a
-VI
a 58
9
Ia
B
. 250
-260
" 2
38
,27
1,2
72
,37
6,1
14
0
d
B. 2
54-2
55"
/753
5
5,7
2,7
84
,81
4
III
c B
. 132
-133
"/1
6 1
19
,12
0,1
04
6
d
B. 1
23'/1
2 3
,26
5,2
72
c,d
B
.140
"/7
22
6
In c
-VII
I 10
46
Vb
3
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Pic
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Hyd
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M. 1
60-1
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Hyd
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M.
126-
127"
Hyd
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M. 1
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18
19
20
21
22
23
24
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51
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M
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Der
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ives
N
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32
33
34
35
36
CH
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11
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125-
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b
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121"
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89
111
b
B. 1
11-1
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3
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57
Pic
rate
: M
. 13
9"
Pic
rate
: M
. 14
1-14
2";
148"
Pic
rate
: M
. 15
5. 5
"
Pic
rate
: M
. 15
5"
Pic
rate
: M
. 17
4-17
6.
5"
Pic
rate
: M. 18
7-18
7.5"
Pic
rate
: M
. 15
0-15
1"
Pic
rate
: M. 15
2-15
3"
Pic
rate
: M. 1
36-1
37"
41
C
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42
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43
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44
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45
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50
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63
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191-
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191"
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63
B.
191-
192"
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63
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M.
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89
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178"
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M.
62.5
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9
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193-
194"
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63
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182"
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57
63
M.
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187"
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63
M.
127-
128"
96
Pic
rate
: M
. 13
7"; 1
41"
Pic
rate
: M
. 12
8-12
9"
Per
chlo
rate
Pic
rate
: M
. 12
8-12
9"
Pic
rate
: M
. 12
5-12
6"
Per
chlo
rate
Per
chlo
rate
: M
. 10
9-11
1"
Per
chlo
rate
: M
. 21
5-21
6"
Per
chlo
rate
: M
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3-18
4"
Pic
rate
: M
. 14
1-14
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TA
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(con
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N.
R
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51
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Pic
rate
: M
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M. 180"(d)
Pic
rate
: M
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; 114
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r: M
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4"
Pic
rate
: M
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0. 5
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Pic
rate
M.
90-9
3"
476
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cn
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Ref
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Der
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68
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66
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I: M
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II
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M. 2
55-2
56"
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C
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CH
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M. 2
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CH
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R
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M. 1
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103"
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5"
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11
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213"
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120-
123"
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M.
140-
141"
M.
136.
5"
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128"
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M. 1
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M. 1
07-1
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M. 7
1"
M. 6
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67"
M. 6
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23
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0,9
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M. 1
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4
M. 1
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M. 2
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.H
NO
,: M
. 168
"
M. 1
74"
938
Pic
rate
: M
. 207
-208
"
Fla
vian
ate:
M. 1
94-1
95"
m m m“ m m
v
m 3 W
N 3 i
i i 3
W N i
ln N 3
I I
2 2 s
m m m m m 01
m m m
b r3 3
z!
m m m
& t- I
m t-
i
E
m m 0.
& N 3
I 0, rl rl
i
Ei *
m m * m m
m
i m ;b 0 r+
g i
m m * m m m m m m 0 N m
3 m 4 I
0 m i
zi
E E d i
m
N i
547
TA
BL
E 2
3a. (
con
t.)
cn
,D
N.
R
R'
R"
X
M
eth
ods
of
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
13
C
H,
14
C
H,
15
CH
,
16
C
H,C
6H5
17
C6H
5
H
H
CH
,CH
, C
ON
H,
CH
,CH
,CH
,CH
, C
ON
H,
C6
H5
C
OO
CH
,
CO
OC
,H5
PH
-C
hH
N0
,
CH
,C6H
5 C
ON
H,
CH
, C
OC
l
CO
OC
H,
CO
OC
,H5
VII
I M
. 233
"
Ia
M
. 76-
82"
Ia
M
. 89-
90"
Ia
M
. 58-
59"
Ia
M
. 65-
66"
M. 5
0.5
-51
.5"
Ia
M
. 121
-122
"
Ia
M
. 177
-180
"
XX
V~
~
.9
4~
xxvr
~
.74
-75
0
xxv
r M
. 73.
5-74
.50
M. 6
1.5-
62"
943
733
491
54
67
938
316
92
54
,92
92
m * m
*- * w 0 N m t - N " N N t- w m m m w
& m N
z-
0 0 3 t - t - g 0 N w * * * m
N * N N w w
0 N m m * m
rd d d e3 c( CI
d CI
X
VI
31W V
D? V
D? u
m rl m 4
0 3 N N
549
m
d 0, pr
N
3
t- m
pr N (D
0 W N
N W N
I
i
d n
d z 0 V
t7
in
% : s V
m 5: V
pr N
0 0 t - w - 3 ,--.
-a
d m i
v 3 3
I t
L- m N
s A d L - 3 3 3
s s s
rd Y
d X
cd 3
d d 3 u
r" V m z
LD
XW V
r" V 51
LD
z? V
m N t- N
m N
0 3 m m
m N 0 3
co 3
rd 3
N W m n
X m X X
W m ln m * W
X 0
t- m 0 * m a ,
m m
5 5 1
m
(D *
m m m m m m
m
m m m m m m
N v) 3
3 In 3
I
r:
3:
co *
w m w m c o m
X 3 1 3 :
0 3 v ) L n m *
5 5 3
TA
BL
E 2
3b.
Py
razo
le-1
-Car
boxy
lic
Aci
ds w
ith
Una
ssig
ned
Str
uctu
re, a
nd t
hei
r F
unct
iona
l D
eriv
ativ
es
N.
R
R'
R"
Met
hods
of
X
synt
hesi
s M
.p.
or
B.p
. R
efer
ence
s D
eriv
ativ
es
5 C
H,
H
6 C
H,
H
7 C
H,
H
8 C
H,
H
9 C
H,
H
H
CO
NH
,
H
CO
NH
,
H
CO
NH
,
H
CO
NH
,
CH
,CH
,CH
, C
ON
H,
C(C
H,)
, C
ON
H,
CH
,CH
,CH
=C(C
H,)
, C
ON
H,
'CiH
5 YH
M. 9
3"
Ia
M
. 90
"
Ia
M
. 78
-79"
XX
Vf
M.
148"
Ia
M
. 95
"
M.
113-
114"
Ia
M
. 88-
89'
Ia
318
751,
752
751,
752
452
191
318
603
320
.HN
O,:
M.
185"
CO
NH
, I
a
M. 1
69-1
7Oo(
d) 1
054
d 10
54
W W w
cd n
m
cd U
0 3 rl rl
W W *
t- 0 Q)
W W w
rd n
r. m U
+g 0
cd U
m
% u
m
d U
F3 rl
LL? u
cd H
N
m 2 8
ri m 3 0 I
m m u
555
TA
BL
E 23b.
(con
t.)
cn
cn
OJ
N.
R
R'
Met
hod
s of
R
"
X
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
M. 1
33-1
34"
10
25
16
H
(CH
,),C
H
CH
, C
Hy
CO
NH
, I
a
\/ \
/
C -
CH
-CH
/
\
17
CH
,
18
CH
3 -C
HZ
CH
,C=C
H-
I CH
,CH
,
19
CH
, -C
(CH
,),C
H,C
=CH
--
I CH
,
CO
NH
,
CO
NH
,
CO
NH
2
Ia
Ia
Ia
M. 1
20"
43
3,43
4
M. 1
65"
Id)
174
M. 1
24"
91
9
20
CH
,CH
, -C
HzC
HZ
CH
ZC
Hz-
C
ON
H,
Ia
M
. 126
-127
"
173
21
C6H
, - C
H2C
HZ
CH
2CH
z-
CO
NH
, I
a
M. 1
64"
13
4
CO
NH
C,H
, X
XV
f M
. 115
-116
"
134
TA
BL
E 2
4.
N-U
nsu
bst
itu
ted
Py
razo
le-3
(o
r 5
)-C
arh
ox
yli
c A
cid
s an
d t
hei
r F
un
ctio
nal
Der
ivat
ives
.
N.
R
R'
X
Met
ho
ds
of
syn
thes
is
M.
p. o
r B
. p.
R
efer
ence
s D
eriv
ativ
es
1H
H
C
OO
H
CO
OC
H,
CO
OC
,H,
CO
N(C
H,C
H,
),
CO
NH
CH
,CH
,N(C
,H,)
,
- C
ON
HC
H,C
H,N
CO
NH
NH
,
Va
VI
a-I1
1 d
VI
a-V
III
XV
II a
XX
V h
I1 a
I1 c
I1 a
VII
I
VI
a
VII
I
VII
I
VII
I
VII
I VII
I
VII
I
M.
210-
212"
M.
215"
M.
141"
M.
16
0
M.
67,
5-68
"
M.
147-
149"
M.
159-
160"
M.
70"
M.
120-
121"
M.
175"
M.
166-
168"
506
Ag
-sal
t
217
Cu
-sal
t
59,
75,
76,
519,
82
9
21
3,4
05
,54
8,8
92
,89
4,1
08
8
506
863
461,
504
863,
864
78
0
59
518
78
0,1
13
5
78
0
367
36
7
561,
864
a
Pic
rate
: M
. 16
5"
Dip
icra
te:
M.
182"
m m N
0 0
O d N t - N i
I / m o i t - N 3
$ 2
5 5
2 r u 0 0 0 0 v v
s
c
N
e m i I
m m i
s
0 (D t- m a +
TA
BL
E 2
4. (
co
d)
UI
Met
hod
s of
m
0
N.
R
R'
x sy
nth
esis
M
. p.
or
B.
p.
Ref
eren
ces
Der
ivat
ives
I a
-Ill
a
XV
II a
CO
OC
H,
CO
OC
,H,
la
VII
I
CO
NH
, V
III
CO
N(C
H,
), V
III
CO
N(C
,HS
),
VII
I
CO
N(C
H,C
H,C
H,)
, V
IIl
0
/C*,
C%
\
'.cH,cH
,/ C
ON
,
CO
NH
C,H
, V
IlI
CO
NH
NH
, V
III
CO
NH
N=
CH
C,H
, V
III
-CO
NH
h-l
H
(I> Or113
V
III
CO
NH
N=
CH
C'H
=C
HC
,H,
VII
I
CO
NH
N-C
(CH
, ),
VII
I
/CH
3 V
III
-CO
NH
N-C
-CO
NH
N=
CH
V
III
I I I 1
H - C
--O
H
HO
- C
-- H
H-C
-OH
CH
,OH
M.
75-7
8"
M.
82-8
3"
M.
178-
179"
M.
136-
137"
M.
151-
152"
M.
162"
M.
183"
M.
153-
154"
M.
237-
239"
M.
258-
260"
M.
258"
M.
23
9
M.
217"
M.
188-
189"
0"
10,4
99,6
27,
629,
893
, 98
8
60
326,
548,
1088
778
76
6,7
80
78
0
78
0
78
0
3 59
766
32
6,7
78
778
778
778
778
778
778
Dia
cety
l d
er:
M.
173-
174"
a m c - m t - t -
t- m * N N 3 +
L- ii m o w w m 0 0 m o w m m w w m 3 - 3 m a m
w w - d g l v m m W N m m m i 3 L - m t - c - t - m m
m e V
X
- i m m z
t- 4 m w , - I +
m m 0 4 3 N
X
4 N
X
N ea
561
TA
BL
E 2
4. (
cant
.)
vl
Met
ho
ds
of
m
N N.
R
R'
X
syn
thes
is
M. p
. o
r B
. p.
R
efer
ence
s D
eriv
ativ
es
-
23
H
24
H
25
H
26
H
27
H
28
H
C6
H5
C
OO
H
9
OH
CO
OC
H,
CO
OC
,H,
CO
NH
NH
,
C O
OC
,H ,
CO
NH
NH
,
la
la
f
VII
I
XV
II a
Ib
I1 a
Ia
I1 a
V
III
Ia
If
\'I11
VII
I
Ia
If
VII
I
M.
198-
199"
M.
231-
232"
M.
235-
237"
M. 26
2"
M. 17
7-17
8"
M. 1
81-1
82"
M. 14
0"
M.
205"
M.
123-
124"
M. 31
0-36
5"(d
)
M.
222"
M. 1
33.
5"
M.
275"
M.
215"
M.
281"
457
247,
550
,
30
1
78,2
16,2
27
771,
955,
988
320
520
216
78,2
27
216,
535
22
1
92 5
925
925
846
846
302
302
36
9
Cu
-sal
t: M
. 32
0"
Hy
dra
zin
e sa
lt
CO
OC
,H,
Ia
M
. 19
1"
36
9
29
H
.H
,O:
M.
219"
. C
OO
H
CO
OC
,H,
CO
NH
NH
,
VIII
Ia
M
. 13
2-13
4"
I a-
VII
I M
. 19
5-19
6"
775
17
5
715
30
H
C
OO
H
CO
OC
,H,
VII
I M
. 25
0"
Ia
M.
162"
31
H
I
a-V
III
M.
235"
C
ON
HN
H,
QfH
3 C
ON
HN
H,
H3C
C
OO
CZ
H5
I
I a-
VII
I M
. 23
9"(d
) 3
92
32
H
33
H
CO
OH
CO
OC
,H,
CO
NH
NH
,
XV
II a
M
. 30
8-31
0"(d
)
VII
I M
. 17
0"
VII
I M
. 26
0"
43
1
275
215
Pic
rate
: M
. 24
2-24
5"
a
CO
OH
X
VII
a
M. 3
28"
364
34
H
35
CH
, C
H3
CO
OH
CO
OC
H,
VII
I M
. 21
6-21
1"
VI
a M
. 14
0-14
2"
XX
VII
I
I1 a
M
. 14
5. 5
"
60
60
25 a
154,
755
01
8
36
CH
,OH
37
C
H,
CH
,OH
C
OO
C ,H
5
VII
I M
. 26
5-26
1"
CH
,CO
OH
C
OO
H
198
TA
BL
E 2
4. (
con
t.)
cn
m
N.
R
R'
X
Met
hod
s of
sy
nth
esis
M
. p. o
r B
. p
. R
efer
ence
s D
eriv
ativ
es
,@
38
CH
, -c
HaC
,C
H,C
H2
CO
OH
"
>O
CO
OC
2H,
\CH
,CH
,
39
CH
, 'G
HS
CO
OH
CO
OC
, H,
CH
,CH
3 C
OO
H
C O
OC
,H
40
CH
,CH
3
41
CH
,CH
,CH
3 C
H3
42
C,H
, C
H,
43
C,H
,
44
CG
H,
CH
,CH
3
CG
H,
CO
OH
CO
OC
,H,
CO
OH
CO
OC
H,
CO
OC
,H,
CO
OH
CO
OC
,H,
CO
OH
VIII
M. 235-236"
VII
I
VI a-VIII
M. 234-236"(d)
VIII
M. 248-250"
la
M. 102-103"
VII
I M. 194"
11 c
B. 135-140"/5
VIII
M. 245"
I1 c
B
. 142-144"/3
VIII
M. 265"
Xa
M. 154"
XXVIII
I1 c
M
. 12
2"
B. 165-173"/3
VII
I M. 241"
I1 c
M
. 127-128"
B. 155-165"/3
111
a
M. 261"
198
198
59
59
205
817
817
817
817
498
25 a
817
817
817
29
.HC
l: M
. 160-161"
N t- N
2
m 4 N
565
w w w m m m
w w m m
in
5 8 8 m u
u u
i m N m
m m w w
4 3 8 u u
m W
w t- N
z'
m m
566
CO
OC
,H,
Ia
M
. 11
0-11
1"
B.
20
8-2
10
"/1
4
63
56
-CH
(CH
~)C
H~
CH
(CH
,)C
H~
- C
OO
H
CO
OC
H,
CO
OC
,H,
57
Q
-H2C
59
CO
OH
CO
OC
,H,
CO
OH
CO
OC
,H,
CO
OH
CO
OC
H,
VII
I M
. 26
9-27
0"
VII
I M
. 9
0-9
1"
B.
197"
/12
Ia
B
. 19
7"/1
2
VII
I M
. 31
0"(d
)
Ia
M
. 1
73
-17
4"
I a-
I11
a
Ia
M
. 25
5-25
8"
I a-
111
a M
. 26
1-26
2"
I a-
I11
a M. 9
1 -9
2"
111
c-X
a-
-VIl
I
VII
I M
. 29
8"
111
c-X
a
Xa
M. v
ery high
la
M. 27
3-27
4"(d
)
63
63
63
89
9
89
9
605
998
997,
998
998
30
30
30
30
275
a
.HC
1: M
. 15
6"
TA
BL
E 2
5.
Pyr
azol
e-3-
Car
box
ylic
A
cid
s an
d th
eir
Fu
nct
ion
al D
eriv
ativ
es
N.
R
Met
hod
s of
R
' R
" X
sy
nth
esis
M
. p.
or
B.
p.
Ref
eren
ces
Der
ivat
ives
1 C
H,
H
H
CO
OC
H,
2 C
H,C
,H,
H
H
CO
OC
,H,
3 C
6H5
H
H
CO
OH
CO
OC
H,
CO
OC
,H,
CO
NH
NH
,
CO
N,
CN
H
H
H
H
CO
OH
CO
OH
IV a
B
. 12
0"/9
54
IV a
M
. 75-
76"
519
B.
150-
160"
/0.6
I11
d
M.
143-
146"
VI
a-X
VII
a
VII
I
XV
II a
I1 f
M
. 72"
VII
I M
. 17
"
111
d
VII
I
VII
I M
. 13
8"
VII
I M
. 74
"(d)
I1 f
272
36
,96
2
881,
963
35,
119,
272
48
9
27
2,8
81
,96
3
963
347
347
347
488
XV
II a
M
. 19
3"
77
0
VII
I M
. 231
"
311
6 C
H,
C6
H5
C6
H5
10
C
6H,
11
-1
12
C6H
,
13
CH
,
H
C6
H5
H
CH
, H
CH
,CH
, H
CH
,(C
H,)
,CH
, H
CH
,(C
H,)
,CH
, H
'BH
S
H
H
CH
3
CO
OH
Co
cl
CO
OC
H,
CO
NH
,
CO
NH
C 6
H5
CO
OH
CO
OC
H,
CO
OC
2H5
CO
OH
CO
OH
CO
OC
,H,
CO
OH
CO
OC
,H,
CO
OH
CO
OC
,H,
CO
OH
CO
OC
,H,
CO
OH
CO
Cl
CO
OC
H,
IV a
VII
I
IV a
VII
I
VII
I
IV a
XV
II a
VII
I
VII
b
VII
I
VII
b
VII
I
VII
b
VII
I
Ia
Ia
IV a
VII
I
VII
I
IV a
M. 171"
M.
73 -7
4"
M.
37-3
8"
M.
158-
160"
M.
94"
M.
132"
M.
122-
123"
M. 1
70"
M.
129"
M.
69"
M.
119"
M.
46"
B.
220"
/2
M. 1
19"
M. 55
"
M.
227-
228"
M. 1
76-1
78"
M. 6
0"
B,
120-
125"
/13
60,
884
Ag
Sal
t
887
60
887
887
95
95
95
16
9
416
416
416
416
416
416
808
808
884
312,
884
71
887
.H,O
. M
. -1
00"
M. 71
.5-7
2.5"
71
,312
.C
H,I:
M. 17
2"
W 02
i e
5
j h:l I I m
m i
t- i
570
0 m
I m t-
2
w m 3
m m X X
0 N 3 N N N m
N
5 7 1
H
H
TA
BL
E 2
5. (
cont
.)
Met
hod
s of
N.
R
R'
R"
X
syn
thes
is
M. p
. o
r B
. p.
R
efer
ence
s D
eriv
ativ
es
CO
OC
,H,
la
77
0
24
0.
H.
-
CO
OH
VIII
M.
160-
180"
7
70
25
CO
OH
la
M.
216-
217"
35
5, 6
02,
96
9
VI b
M. 2
29-2
31"
527
VIII
355,
527
, 96
9
XVII a
M. 1
22-1
24"
548
CO
OC
H,
Ia
M.
174-
175"
52
7,77
0
M.
182-
183"
CO
OC
,H,
I a
M.
78-7
9"
96
9
WV a
M. 9
6-9
7"
355
28
ON
02
29
e2
do,
30
O
N0
2
902
31
O
H.
H
CH
3 C
OO
H
Ia
M
. 239
-241
" 60
2
CH
,CH
3 C
OO
C,H
, I
a
M.
91"
533
CH
,CH
3 C
OO
H
Ia
M. 19
3"
533
M.
181"
53
3 C
H,(
CH
,),C
H,
cOO
C,H
, I
a
CH
,(C
H,)
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, C
OO
H
Ia
M
. 15
0"
533
CO
OC
,H,
Ia
M. 1
65"
533
CO
OH
V
III
M.
290-
292"
7
70
m m
2
0 c- t-
m
N m
2
rd I
X
N m
m m 0 - m m m m m
W
m m W W m m
m W m m m iD N W w
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l l
m m v)
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v-v
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in
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m
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c-4 LC i Ln 0 m m d
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5 7 5
TA
BL
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5. (
con
t.)
01
Met
hod
s of
N.
R
R'
R"
X
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
4
56
C,H
,
57
C,H
,
58
C,H
,
*,H, C
OO
H
VII
I -
H
CO
OC
,H,
Ia
HJa: C
OO
C,H
, I
a
CO
OH
V
III
H
CO
OH
V
III
CO
OC
,H,
Ia
H
59
C
,H,
n C
OO
H
VII
I
CO
OC
,H,
Ia
C O
OH
V
III
CO
OC
,H,
I a
61
C
,H,
H
c H3
CO
OC
,H,
Ia
CO
OC
,H,
VII
I C
H3
M. 20
8"
M.
126"
M.
195"
M. 8
1"
M. 2
15"
M.
168"
M. 1
66"
M. 98
"
M.
253"
M. 1
15
-11
7"
M. 2
18"
M. 1
51"
M.
15
7-1
59
"
36
9
36
9
912
Ag
salt
912
37,
912
37
77
5
77
5
77
5
775
36
8
36
8
10
76
10
76
W P- O 3
3
(D 3
I 0 W 3
2
z? V
21
(0 c- 0 d
(D c- 0 d
W c- 0 3 d
t- 3 d P- 3
m 2 0 N
I I 0 0 N
I
3
c- 3
0 c- 1
0) 3
v m 1
2 2 2
rd
2 x
X
3:
0
4 LJ
Xrn V
Ern u
m 0 W P-
m W P- W 9 u3 W
W (D 10
TA
BL
E 2
5. (
cont
.)
cn 4
mN
R
M
eth
od
s of
R
' R
" X
sy
nth
esis
M
.p. o
r B
.p.
72
CH
,
73
CH
,
74
CH
,
75
C
H,
76
CH
,
77
CH
,
78
CH
,CH
,
79
CH
,CH
,
--C
H,C
H,C
H,-
-cH
,CH
(CH
,)C
H,-
-CH
,CH
,CH
,CH
, -
-CH
,CH
,CH
,CH
(CH
, 1 -
-CH
,CH
(CH
~)C
H,C
H, -
- C
H2C
H,C
H, -
-CH
,CH
,CH
,CH
,
CO
OH
CO
OC
H,
CO
OC
,H,
CO
OH
CO
OC
H,
CO
OC
,H,
CO
OH
CO
OC
H,
CO
OC
,H,
CO
OH
CO
OC
H,
CO
OH
CO
OC
H,
CO
OH
CO
OC
H,
CO
OH
CO
OC
H,
CO
OH
VII
I
VII
I
Ia
VII
I
VII
I
Ia
VII
I
IV a
VIl
I
Ia
IV a
-VII
I
VII
I
I a-
VII
I
IV a
-VII
I
VII
I
IV a
-VII
I
VII
I
VII
I
1V a
IV a
-VII
I
M.
208"
(d)
M.
96.
5-97
"
M.
175-
175.
5"
B.
i3n
-i4
0a/
iz
M.
208.
5"
M.
87-8
8"
B.
194"
/12
M.
170.
5"
B.
18
5-i
87
~/i
i
M.
114-
115"
M.
176-
177"
M.
73 -7
4"
Ref
eren
ces
Der
ivat
ives
86
86
86
86
86
63,
97
63
,97
63,
97
63.
97
63
63
63
63
63
63
63
63
63
63
CO
OC
H,
VII
I M. 1
08-1
09"
63
--C
H~
CH
,CH
~C
H(C
H,)
- C
OO
H
CO
OC
H,
CH
,CH
(CH
,)C
H,C
H,
-
CO
OH
CO
OC
H,
IV a
-VII
I
VII
I
M.
127.
5-1
28.
5"
B.
182-
183"
/10
63
63
80
CH
,CH
,
81
C
H,C
H,
82
CH
,CH
,
.H,O
: M
. -9
4"
IV a
-VII
I
VII
I
M. 1
47.5
-149
. 5"
M. 44
. 5-
45.
5"
63
63
CH
(CH
,)C
H,C
H(C
H,)
CH
, -
CO
OH
CO
OC
H,
M.
141-
141.
5"
M.
64.5
-65.
5"
B.
188-
189"
/11
63
63
IV a
-VII
I
VII
I
83
CH
,C,H
,
84
CH
,C,H
,
85
C
H,C
,H,
86
CH
2C,H
,
-CH
,CH
,CB
,CH
, ~
CO
OH
CO
OC
H,
M.
157.
5-1
58.
5"
M.
69-7
0"
63
63
IV a
-VII
I
VII
I
-CH
,CH
,CH
,CH
(CH
,)
-
CO
OH
CO
OC
H,
-CH
~C
H(C
H,)
CH
,CH
, -
CO
OH
CO
OC
H,
-CH
(CH
,)C
H,C
H(C
H,)
CH
, ~
CO
OH
CO
OC
H,
IV a
-VII
I
VII
I
63
63
.H,O
: M
. 11
9-12
1"
B.
242-
246"
/11
M. 1
43.
5"
M.
98-9
9"
IV a
-VII
I
VII
I
63
63
IV a
-VII
I
VII
I
M.
137-
138"
M.
112-
113"
B.
242-
243"
/11
63
63
86,4
16
86
86
416
87
C,H
,
01 4
W
-CH
ZC
HZ
CH
2-
CO
OH
CO
OC
H,
CO
OC
2H,
VII
I
VII
I
Ia
VII
b
M. 2
16.
5"
M. 14
0. 5
"
M.
143"
M. 2
20"
CO
OH
V
III
416
TA
BL
E 2
5. (
con
t.)
En
m 0
N.
R
R'
R"
X
CO
OC
,H,
89
C
,H,
- C
H2C
H,C
H,C
H2 -
CO
OH
90
91
C,H
,
92
C,H
,
93
C,H
,
94
C,H
,
CO
OC
H,
CO
OC
2H,
CO
OH
CO
OC
2H,
CO
OH
CO
OC
H,
CO
OH
CO
OC
H,
CO
OC
,H,
-CH
(CH
,jC
H,C
H(C
H,)
CH
, -
CO
OH
CO
OC
H,
-CH
2CH
2CH
2CH
,CH
2 -
-CH
2CH
2CH
,CH
2CH
, -
CO
DH
CO
OC
2H,
CO
OH
CO
OC
,H,
Met
hod
s of
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
VII
b
M.
119"
41
6
Ia
M
. 16
3-16
4"
48,
97
VII
I 41
6
VII
I M
. 10
9-11
0"
48
VII
b
M.
99"
416
VII
I M
. 221
" 41
6
VII
b
M.
138"
41
6
I a-
VII
I M
. 17
7-17
8"
63
VII
I B
. 23
8-24
0"/1
2 6
3
VII
I M
. 19
6.5-
198.
5"
6
3
VII
I M
. 11
9-12
0"
63
Ia
M
. 128
-129
"
63
I a-
VII
I M
. 19
3. 5
" 63
VII
I M
. 87
-88"
63
B.
240"
/11
VII
I M
. 16
2"
VII
b
M. 9
5"
VII
I M
. 205
"
VII
b
416
416
416
116
( D L D
b V 3 3
a m a 0 0 m m m 0 0 m m m m m
m m a m m m m m m m m m
m m m m P J,
58 1
cn
N
m
N.
R
R'
R"
TA
BL
E 2
6.
Pyr
azol
e-3
(or
5)-C
arb
oxyl
ic A
cid
s (w
ith
Un
assi
gned
Str
uct
ure
) an
d t
hei
r F
un
ctio
nal
Der
iva
tiv
es
-
1 C
H=C
HC
OO
CH
, H
C6
H5
C6
H5
5 C
6H5
6 C
6H5
C6
H5
H
H
H
H
H
H
H
CH
,CH
,
CH
,CH
,
CH
,CH
,CO
OH
CH
,CH
,CO
OC
,H,
CH
,CH
,CH
,CH
,
CH
,CH
,CH
,CH
,
X
CO
OC
H,
CO
OH
CO
OC
,H,
CO
OH
CO
OC
,H5
CO
OH
C O
OC
, H
CO
OH
CO
OC
,H
CO
OH
CO
OC
,H5
CO
OH
CO
OC
,H5
Met
hod
s of
sy
nth
esis
M
. p.
or
B. p
. R
efer
ence
s D
eriv
ati
ves
I1 a
-IV
a
IV a
VII
I
Ia
VII
I
la
VII
I
Ia
VII
I
Ia
VII
I
Ia
Ia
Ia
M.
110-
110.
5"
M.
135-
136"
B.
125-
127"
/3
M.
140-
141"
B.
152-
154"
M. 1
65-1
67"
M.
83-8
4"
M.
13
7-1
39
M.
59-6
0"
Dec
. 18
5"
M. 2
04"
M.
186-
87"
863
863
1001
1001
1001
1001
1043
, 104
9
10
43
,10
49
241
241
601
601
601
601
Na
salt
m m m m N N N m m m m r(
ro 0 3
2
I
P
i ln N
I 0 v) N
- m m N
u' B
X
m N i d 3 0
i
583
TA
BL
E 2
la.
Pyr
azol
e-4-
Car
box
ylic
A
cid
s an
d t
hei
r F
un
ctio
nal
Der
iva
tiv
es
N.
R
R'
X
Met
hod
s of
R
" sy
nth
esis
1H
H
2 C
H,
H
3
CH
2C6H
, H
H
CO
OH
H
CO
OC
H,
CO
OC
,H5
CO
OH
H
CO
OH
H
CO
OC
,H,
CN
CO
OH
CO
OC
H,
CO
OC
,H,
H
111
a b, d
Va
c6
YV
II a
VII
I
la
VIl
l
V c
6
XV
II a
VII
I
VII
I
V c
6
III
d b, d
VII
I
XV
II a
II f
la
VI
a b
M. p
. or
B.
p.
M. 2
70-2
75"
M.
278-
279"
M.
76-7
8"
B.
120-
130"
/0.6
M. 2
05-2
06"
M.
208-
209"
(d)
M.
151-
152"
M. 6
2-63
"
M.
63-6
4"
M.
214-
215"
M.
221-
222"
M.
128-
129"
M.
96-9
7"
M.
99-1
00"
Ref
eren
ces
__ -
20
8,2
09
211,
548
, 55
2
515
506
278,
515
515
518
515
506
383,
506
515
515
515
266
57
2,6
35
1045
115,
11
6,3
80
,94
9
1045
, 1
04
6,1
04
7
48
8,4
89
35
3,8
09
1111
1046
10
45
,10
46
,10
47
Der
iva
tiv
es
Ag
salt
10
H
cn
m
UI
'tjH
5
CN
CO
OC
,H,
COOH
COOCZHS
CN
C O
OH
COOC,H,
CN
CN
COOH
CO
OC
,H,
C ONHC fi H
,
CO
N11
<>C
H, 01
H5
COOH
C-H
, COOC,H,
CONHC,H,
H
H
H
H
VI
a
VlI
I
Vl
b
XV
II a
vi a
Vi
a
VII
I
XV
II a
VI
a
VIl
l
Vi a
VII
i
VI
a-vm
I
a
VII
I
la
13
Ia
VIE
I1 a
Id
Ia
M.
95"
M.
133-
134"
M.
253-
254"
M.
161-
162"
M. 1
62-1
63"
M.
250"
.
M.
183-
184"
M.
190-
191"
M.
174-
175"
M.
228Y
d)
M. 54
"
M.
179"
M.
179"
M.
163"
M.
260"
12
,11
10
383,
797
1046
1047
3 84
12
12
12
12
1111
12
12
,11
10
12.1
110
59, 7
5, 7
6, 8
30
307
.H,O M
. 46
"
165
.HC
L M
. 16
0"
307
307
307
308
M.
111.
5-11
2.5"
96
M.
85-8
6"
308
M.
182"
30
8
HCI: M. 20
0"(d
)
* F
rom
met
hyl (01. et
hyl)
fo
rmy
l-ac
etat
e ph
enyl
(o
r p.
brn
mop
heny
lj-h
ydra
zone
by
low
-pre
ssu
re d
isti
llat
ion
x
!Y
586
s, m s m m a
m 3 1 O W f 2 - 3 3 m 3
c d
6 0
W E q q a .c
$6 4
C
fix ;- 31
c N
iD t - m N N N
587
W 0 0 W 0 Fa
0 0 t- e 3
r.2 2
V 3
V -
3 z 0 0
I I
d id
588
32
C6
HS
H
35
CH
3 C
H3
36
CH
3 C
H3
37
CH
, c6
11S
38
CH
zOH
C
6H
5
- @a 39
C,H
, C
H3
(D
0C21
l5
CN
CN
CO
OH
CO
OH
CO
OH
CO
Cl
CW
*H
S
Id
M. 165"
306
Id
M. 118"
309
Id
M. 182"
459
Id
M. 212"
459
I11 b
M. 248"
41 1
C
6H
S
CH
II
I b
M
. 199-200"
235
CH
VIII
V c6
XVIl a
VIU
CO
NH
,
CO
NH
C6H
,
CO
OH
C
6H
5
CO
OH
C
H3
CO
OC
H,
CO
OC
,H,
CH
3
CO
OH
C
H3
la
IV a
VII
I
VII
I
M. 217"
887
506
450
887
887
M. 37"
887
M. 200'
887
M. 15
9"
887
M. 61-68"
B. 140-150'712
IV a
M. 176-177'
884
Ia
M. 197-198"
884
IV a
884
IV a
-VII
I M. 63
-64"
884
IV a
M. 110-112"
913
Anhydride: M. 143"
VIII
M. 194-196"
145, 546,869,979,1024
Ag
sa
lt
XVII a
M. 200-201"
385,450
K s
alt
Anhydride: M
. 189.5"
885
x
L
p:
i
590
49
C,H
, C
H,O
C,H
,
50
C
,H,
CH
,
53
C,H
, C
H,
54
C,H
, C
H,
54
CO
OH
CO
OH
CO
OC
H,
CO
OH
CO
OH
CO
OH
CO
Cl
CO
OC
*H
,
CO
NH
CN
CO
OH
CO
OC
ZH
S
CH
3
CH
,CO
CH
,
CO
OC
<CH
', 'C
H-
Id
VII
I
VII
I
la
I a-
VII
I
I a-
VII
I
VIE
XV
ll a
VlI
I
la
d
VI
a
VU
I
VIU
Ia
d
VII
I
VII
l
Ia
VIU
M
178'
M
17
8-1
79
'
M
125
M. 1
58"
M.
88"
M.
18
5"
M. 2
05'
M. 78
. 6-
80.
1"
M. 19
3-19
4.
5"
M. 1
89
"
M.
218"
M.
225"
(d)
M.
146"
M.
146'
148
143
143
14
3,9
78
183
183
141,
562,
567,
10
86
385
824
14
1.
562,
567
, 10
85
824,
971
, 11
25
80
129
82
4
239,
759
824
824
569,
803
567,
569
,727
569
Ag
sa
lt
Oxi
me:
M.
20
9-2
11
"
Ph
enyl
hyd
razo
ne:
M
222'
Ph
enyl
hyd
razo
ne:
M. 2
65-2
66'
Ag
salt
: M
. 22
2'
K s
alt
Ag
salt
TA
BL
E 2
7a.
(con
t.)
Ln
m
X
N.
R
R'
R"
56
C6H
5
57
C,H
,
58
C6
HS
59
C,H
s
60
C,H
,
61
C
,H,
62
C,H
,
63
C,H
,
64
C6
H5
Q
--('a
s
CO
OH
CO
OH
CO
OC
,Hs
CO
OH
CO
OC
,H,
CO
OC
,H,
CO
OH
CO
OC
,Hs
CO
OH
Met
hod
s of
sy
nth
esis
VIl
l
VlI
I
VII
I
VII
I
la
VII
I
VU
I
VII
I
VII
I
VIU
la
VlI
I
M. p.
or
B. p
R
efer
ence
s D
eriv
ati
ves
M. 2
61
"
M. 2
08-2
10"
M.
158-
160"
M.
236"
(d)
M.
121-
122'
M.
244"
M.
18
6"
M.
155-
156"
M.
157.
5"
M.
202"
M.
210"
M.
128"
M.
251"
M.
261"
569
129
12
9
12
9
12
9
12
9
12
9
129
12
9
569
567,
569
,727
387,
567
, 56
9
Su
lfon
e: M
. 16
2"
m W rn m m -
t - c t- m m m m
m (0
m m
0 0 s. m U U
in
3 9 U B LD W t- a w W
EW 3 t- m a a
A
m o a t -
593
TA
BL
E 2
7a. (
can
t.)
01
u? R
' X
R
"
N.
R
CO
OH
CO
OC
,H,
73
C
,H,
CO
OH
c-
2H5
I4
C,H
, 's
H5
CN
CO
OH
CO
W 2%
15
C
,H,
<J-
g O
-CH
Z
76
C
,H,
C6
H5
C
ON
H ,
CN
77
C,H
, C
6H
5
78
C
,H,
CG
H5
CN
CO
OH
CO
OC
H,
CO
OC
,H,
CO
NH
____
M
eth
ods
of
syn
thes
is
VlU
XI
a
__
_._
VII
I
XI
a
v1n
XI
a
Ia
VII
I
XI
a
VII
a
VLU
VII
I a
VII
I
XV
lI
Xa
11 e
VII
a
XI
a b
Ie
V
III
M. p
. or
B. p
. R
efer
ence
s D
eriv
ati
ves
M.
17
7-1
78
"
M
88
-89
"
M.
207-
208"
M. 1
05.5
-106
.5"
M.
210"
(d)
M.
10
7-1
08
"
M.
15
8"
M.2
04
"(d
)
M. 9
7-9
8"
M. 21
1"
M. 1
63
-16
4"
M.
205"
(d)
M. 2
38-2
39"
M.
14
0-1
41
"
M.
145-
146.
5'
M. 1
99-2
00"
73
1
73
1
121,
72
9
72
1,1
29
72
7,7
29
721,
72
9
148
73
1
73
1
418
418
418
148
30
4,4
98
,72
8,9
45
385
498
482
41
1
12
8
75
8
304
418
6
9 U
8 8
m N t-
m -r 3
t- W 3
i
z V
4
N a m
595
TA
BL
E 2
7a.
(con
t.)
yl
(D
R'
01
N.
R'
X
Met
hod
s of
D
eriv
ati
ves
R
"
syn
thes
is
M.p
. or
8.p
. R
efer
ence
s
85
C,H
, I
a
M. 81
-02
" 89
7 C
OO
C',H
, C
"3
CO
OH
C
H:,
V
III
M. 20
3'(d
) 7
31
CO
OC
,H,
XI a
M. 94
-95
' 731
B
L
6 k 0
m * Ln W t-
597
Y 3
rd
P
d, a
d,
1
k
x
e:
i l
x x 5: x x
x x &? x x u
N P ?
598
CO
OC
H,
IV a
CO
OC
,H,
Ia
d
CO
NH
, V
III
/CH
, --
c,H
2 -C
O-N
P
' CH
, -C
H,
B.
91"/
11
71,3
12
72
72
887
M.
165"
M. 7
5-76
"
3 59
7 C
H,
H
M. 1
83-1
84"
78
49
,95
95
CO
OH
IV
a
CO
OC
H,
IV a
CO
OC
,H,
IV a
8 C
H,
9 C
H,
H
H
CO
OC
,H,
IV a
M
: 93
O
369
CO
OC
H,
IV a
CO
OC
,H,
IV a
M.
79-8
1"
775
M.
60"
775
10
C
H,
CO
OC
H,
IV a
M
. 11
4"
368
H
H
11
CH
,CH
, C
H3
CO
OH
in
11
CO
OC
,H5
IV a
M.
141-
142"
71
B. 1
01.
5"/1
2 71
P
icra
te:
M. 6
8-69
"
M.
162-
163"
78
B.
193-
194"
/12
78
12
CH
,CH
, C
6H
5
H
CO
OH
V
III
CO
OC
,H,
IV a
H
CO
OH
CO
Cl
CO
OC
zH
M.
140-
141"
35
9
B. 8
9"/1
1 35
9
B.
128-
141"
/23
359
TA
BL
E 2
8.(
con
t.)
m
0
N.
R
0
Met
hod
s of
sy
nth
esis
M
. p.
or
B.
p.
Ref
eren
ces
Der
iva
tiv
es
R'
R"
X
,CH
, --
C,H
, -C
O-N
/o
\c
H,-
-cH
, M
. 85
"
359
H
CO
OH
CO
Cl
CO
OC
,H,
,CH
, - C
,H2
-CO
-N
/o
\CH
,-
CH
,
VII
I
IV a
M.
124"
B.
101-
102"
/11
B.
122"
/11
51
3 59
51
14
CH
,CH
=CH
, C
H3
M. 7
9-80
"
359
M.
99-1
00"
M.
87-8
8"
M.
156"
CO
OH
X
VII
a
988
CO
OH
X
VII
a
988
72
988
72
CO
OH
V
III
XV
II a
IV
a
C O
OC
, H ,
B.
170-
171"
/9
M.
117-
118"
M.
189-
190"
18
C
H,C
,H,
19
C
,H,
H
H
988
CO
OH
X
VII
a
CO
OH
I
a
d
Xd
XV
II a
XX
V b
VlI
I
26
4,2
72
,96
9 A
g sa
lt
72
3,2
64
,26
5
988
962
888
CO
Cl
M.
39-4
1"
B.
160-
164"
/17
N t- N N N w t - r : N
0 r- t- m m W
W co 3 N r- -r
- m a (00 - F a N C U
3 m m
m m I ": 4
0 0
t- 3 N
i
W W
I m W
2
m t- N
2
rd rm rd
a a m m m z
x Y
W N v) cu 3 N 0 N w N m
N N N
601
w 3 m
N N N
I 3 N N
2
rd 3
m : 8 V
51
u,
V X V
I 1
V
c-. N
* m m
0 - 6 o m m w m w m m
t - t -
0 N
X
Xrn V
XW V
m m 3
c- m 3
2
3
s P-
X
V 8
B V
r " r " v v Xm V V
m m o N @ a m
B
m r,
3 N m m
34
C
H,
CH
, C
OO
CH
, M. 1
74-1
75"
20
0
VII
I
35
C
6H5
36
C
,H5
CO
OH
X
XV
III
25 a
M. 20
1-20
2"
M. 1
38-1
40"
CO
OH
CO
OC
,H,
XX
VII
I
XX
VII
I
25 a
25 a
37
C,H
5
38
C
H,
CO
OH
X
XV
III
M. 22
2"
25 a
-CH
,CH
,CH
, C
OO
H
CO
OC
H,
CO
OC
,H5
VII
I
VII
I
Ia
M. 20
0. 5
"
Oil
86
86
86
M. 2
07-2
08"
B.
158-
160"
/14
39
C
H,
CO
OH
CO
OC
H,
Ia
IV a
63,
97
63,
97
CH
,CH
,CH
(CH
, )C
H, -
40
C
H,
CO
OH
I
a-V
III
IV a
-VII
I
M. 1
95-1
95.
5"
63
63
41
CH
,
42
CH
,
43
CH
,CH
,
44
CH
,CH
,
0)
g
45
CH
,CH
,
46
CH
,CH
,
-CH
(CH
, )C
H,C
H,C
H,
--
-CH
,CH
(CH
, )C
H,C
H(C
H,)
-
-CH
,CH
,CH
, ~
-
-CH
,CH
,CH
,CH
, -
-CH
,CH
,CH
(CH
,)C
H,
-
-CH
(CH
3)C
H,C
H,C
H2
-
CO
OH
CO
OH
CO
OH
CO
OH
IV a
-VII
I M. 1
28-1
30"
M. 1
79-1
80"
M. 1
78-1
79"
M. 1
48-1
49"
63
IV a
-VII
I 63
IV a
-VII
I 86
IV a
-VII
I 63
CO
OH
IV
a-V
III
M. 1
84-1
85"
M. 4
3-49
"
63
CO
OH
IV
a-V
III
63
TA
BL
E 2
8.(c
ont.
)
m
,D
N.
0
R
R'
R"
X
41
48
49
50
51
52
53
54
55
56
-CH
,CH
(CH
~)C
H,C
H(C
H,)
-
-CH
2CH
2CH
,CH
, -
-CH
2CH
2CH
(CH
3)C
H, -
-CH
(CH
, )C
H2C
H2C
H, -
-CH
,CH
(CH
, )C
H,C
H(C
H,)
~
-CH
2CH
2CH
2 -
-CH
,CH
2CH
2CH
2 -
-CH
,CH
,CH
(CH
,)C
H,
-
-CH
(CH
, )C
H,C
H,C
H, -
-CH
,CH
(CH
,)C
H,C
H(C
H,)
-
CO
OH
CO
OH
CO
OH
CO
OH
CO
OH
CO
OH
CO
OH
CO
OH
CO
OH
CO
OH
Met
ho
ds
of
syn
thes
is
IV a
-VII
I
IV a
-VII
I
IV a
-VII
I
IV a
-VII
I
IV a
-VII
I
I a-VIII
I a-
VII
I
I a-
VII
I
I a-
VII
I
I a-VIII
~
M.
p. o
r B
. p.
R
efer
ence
s D
eriv
ativ
es
M.
145-
146.
5"
M.
187-
187.
5"
M.
186-
187"
M.
154-
154.
5"
M.
15
9.5
-16
0.
5"
M.
217.
5"
M.
194-
195"
M.
202-
203"
M.
180-
181"
M.
223"
63
63
63
63
63
86
48,
97
63
63
63
TA
BL
E 29a.
Py
razo
le-1
, 3-D
icar
box
ylic
Aci
ds
and
th
eir
Fu
nct
ion
al D
eriv
ati
ves
.
N.
R
R'
Met
hod
s of
X
x'
sy
nth
esis
M
. p.
or
B. p
. R
efer
ence
s D
eriv
ativ
es
1H
C
H3
CO
OC
,H,
CO
NH
,
CO
NH
C,H
,
CO
OC
,H,
CO
OC
,H,
CO
NH
,
2H
C
H,C
H,
CO
NH
,
CO
NH
,
3H
C
H,C
H,C
H,
CO
NH
,
4H
C
H,C
H(C
H,)
, C
ON
H,
CO
NH
,
5H
C
H,(
CH
,),C
H,
CO
NH
,
CO
OH
la
CO
OH
I
a
CO
OH
xx
v f
CO
OC
H,
XX
Vf
CO
OC
,H,
CO
OC
,H,
Ia
CO
OH
la
CO
OC
,H,
Ia
CO
OH
I
a
CO
OH
I
a
CO
OC
,H,
CO
OC
,H,
Ia
M. 174-175"
Dec
. 155"
M. 232-234"
M. 158-160"
M. 82"
B. 178-179"/13
M. 131"(d)
M. 167"
M. 112-113"
M. 165-166"
M. 123"
M. 58-59"
60
600
470
60
67
60
53 2
532
532
53 2
532
532
TA
BL
E 2
9a.
(con
t.)
Met
hod
s of
N
. R
R
' X
X'
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ati
ves
m
m
0
6 7 8 9 10
11
12
CH
,(C
H,)
,CH
,
CH
,(C
H,
),cH
,
CH
, (C
H, )
,cH
,
H
H
CH
3
-CH
,CH
,CH
,CH
,
CO
OH
CO
NH
,
CO
NH
,
CO
OH
CO
NH
,
CO
NH
,
CO
OH
CO
NH
,
CO
OC
, H,
CO
OC
, H
CO
OC
H,
CO
NH
C,H
,
CO
OC
,H,
CO
OC
, H,
CO
OC
,H,
CO
OC
,H
CO
OH
CO
OH
CO
OC
,H,
C O
OH
CO
OH
CO
OC
,H,
CO
OH
CO
OC
,H,
CO
OH
CO
OC
H,
CO
OC
,H,
CO
OC
,H,
CO
OH
CO
OC
H,
CO
OH
CO
OC
, H ,
VII
I
la
la
VII
I
Ia
la
VII
I
Ia
xxv
f
xxv
f
xxv
f
xxv
f
Ia
xxv
f
M. 167"
M.
161-
162"
M.
61-6
3"
M. 1
56"
M.
145-
148'
M.
55-5
6"
M.
139-
141"
M. 6
5-67
"
M.
156-
157'
M. 8
6-87
"
B.
177"
/13
M. 1
5-7
6"
M. 1
05-1
06"
M.
148.
5-1
49.
5"
M. 8
4. 5
-86"
B.
185"
/10
M.
158.
5-1
59.
5"
M.
92-9
3.
5"
53 2
53 2
532
532
532
53 2
532
532
60
60
93
93
58,6
0
97
97
97
TA
BL
E 2
9b.
Py
raz
ole
-l,3
(o
r 5
)-D
icar
bo
xy
lic
Aci
ds
(wit
h u
nas
sig
ned
str
uc
ture
) an
d th
eir
Fu
nct
ion
al D
eriv
ativ
es.
N.
R
R'
X
Met
ho
ds
of
X'
syn
thes
is
M.p
. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
1
H
CH
,(C
H,)
,CH
, C
ON
H,
CO
OH
I
a-V
III
Dec
. 80
-82"
60
1
M.
160-
163"
18
8
2 H
C
H=C
(CH
,),
CO
NH
C6H
5 C
OO
C,H
, I
a
M. 2
38-2
39"
3
H
C6H5
CO
OC
H,
CO
OH
X
XV
f M
. 126
-126
.5"
54
CO
OC
H,
CO
OC
H,
XX
Vf
M.
95"
54
CO
OC
,H5
CO
OC
,H,
M.
80-8
1"
67
TA
BL
E 3
0.
Py
razo
le-1
, 5
-Dic
arb
ox
yli
c A
cid
s an
d th
eir
Fu
nct
ion
al D
eriv
ativ
es
~~~~
Met
hods
of
N.
R
R'
X
X'
syn
thes
is
M.p
.or
B.p
. R
efer
ence
s D
eriv
ativ
es
1
C6H
, C
,H,
CO
OC
H,
CO
OC
H,
Xa
M
. 150
" 29
N N N
s 0" s: 2
a
2 zm m V
3 N m
608
TA
BL
E 3
1a.
Pyr
azol
e-1,
4-D
icar
box
ylic
Aci
ds
and
thei
r F
un
ctio
nal
Der
ivat
ives
.
TA
BL
E 3
2.
Pyr
azol
e-3,
5-D
icar
box
ylic
Aci
ds
and
thei
r F
un
ctio
nal
Der
ivat
ives
~~~
~ ~
-
~~
-----
Met
hod
s 01
N
R
R'
X
X'
syn
thes
is
M p
or
B.p
. R
efer
ence
s D
eriv
ativ
es
1H
H
C
OO
H
CO
OH
xv
n a
M 2
90"
(d )
457,
548
,629
N
a sa
lt
__
_
__
_
__
- - -~
63
1,7
62
,89
3
K s
alt
99
3,1
08
8
Ag
salt
Ca
sal
t
2H
CO
Cl
CO
OC
H,
CO
Cl
CO
OC
H,
/CH
,-\H
, ,C
H,-
-I;F
I,
SO
N
p
=ON,
,O
k
H,
- C
H,
CH
,-C
H,
CO
N,
CO
N 3
CH
, C
OO
H
CO
OH
CO
OC
H,
CO
OC
H,
CO
OC
ZH
5 C
OO
C2H
,
CO
OC
,H,
CO
OC
H,C
OO
H
3H
C
H,C
OO
H
CO
OH
C
OO
H
.m 0
"4
H
CH
,CO
OC
H,
CO
OC
H,
CO
OC
,H,
* F
rom
eth
yl a
-ace
tace
tyl-
hyd
razo
ne
of
tetr
ahyd
rofu
ran
-(%
, 3,4
)-tr
ion
e by
hea
tin
g w
ith
HC
1 30
%.
Ba
salt
M. 3
10
359,
1101
.A
nhyd
ride
:
M. 8
6-87
"
359,
1101
VI
a
M.1
51
.5"
21
7
894
b
M. 1
53"
21
7,8
04
,89
3
VII
I M
. 184
" 35
9,11
01
M. 1
94-1
96"
Dec
. 120
-122
"
561
VI
a-V
III
M. 3
13"
59
Ag
sali
vm
M. 3
15"
37
2,5
04
,10
57
XV
II a
38
9, 5
39, 5
40,
1057
I1 c
M
. 128
-129
"
804
I1 a
M
. 10
6-10
7"
3 72
* M
. 18
1"
1057
VII
I M
. 23
4-23
5"(d
.)
278
I1 a
M
. 109
-110
"
278
TA
BL
E 3
2. (
cont
.)
N.
n R
' X
X'
Met
hod
s of
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
5H
c6
rf5
CO
OH
C
OO
H
I1 a
-VII
I
I1 c
-VII
I
Vl
a
VlI
I
XV
II a
VI
a
VI
a b
XV
II a
IV a
-VII
I
Dec
. 243
-246
"
94
,20
8,2
12
, 552
20
8,2
12
, 552
210
215
389
215
20
9,2
10
221
506
61
359,
1101
359,
1101
359.
1101
CO
OC
H,
CO
OC
,H,
CO
OC
,H,
CO
OC
,H,
M.
104-
105"
M.
96"
6 C
H3
7 C
H,C
H,
H
H
CO
OH
CO
OC
H,
CO
OH
CO
Cl
CO
OC
,H,
M. 250"(d.)
M. 7
2-73
.5"
M. 24
3"
B.
125"
/12
CO
OH
CO
OC
H,
CO
OH
CO
Cl
CO
OC
,H,
/CH
,-C
H,
--C
ON
)O
\C
H,-
CH
, C
H,-C
\H,
CH
,-C
H,
-CO
P(
p
VII
I M
. 12
3"
359.
1101
8 C
H(C
H,)
, C
OO
H
CO
Cl
CO
OC
H,
CO
N(C
H,)
,
M. 2
85"
B.
145-
146"
/17
M.
66"
M. 1
04-1
05"
359,
1101
359,
1101
359,
1101
359,
1101
H
VII
I
M.9
9.5
"
359,
1101
M. 1
47"
35
9,11
01
X m X X X
3 - 0 3 m 3 N 1 - 3
611
TA
BL
E 3
2 (c
ontd
.)
01 -
N.
R
R'
X
X'
Met
hods
of
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
CO
OC
,H,
/CH
,-C
Hz
-CO
N
;o \C
H,-C
H,
/CH
,-C
H,
-CO
N
>o
\CH
,-CH
,
CO
OH
CO
Cl ,C
HZ
--C
HZ
-C
ON
,O \*
\CH
,-CH
,
CO
OC
,H,
CO
OC
,H,
/CH
z-C
H,
CO
N
>o
\CH
,-C
H,
359
359
M.
79"
15
C
H,C
,H,
H
16
C
H,C
H,C
,H,
H
M. 13
9-14
0"
M. 22
4"
M. 8
6"
M. 1
10"
359,
1101
CO
OH
CO
Cl
359
359
359
$2
CH
,-C
H,
17
C
H,C
OC
,H,
H
18
C
,H,
H
CO
OC
,H,
/CH
z-C
H,
-CO
N
>o
\CH
,-C
H,
CO
OH
M. 12
8"
359
359
CH
,-<
H2
CH
,-C
H,
-co<
p
CO
OH
X
VII
a
M. 2
66"(
d.)
112,
246
, 21
2, NHJ s
alt:
M.
210"
53
2
10
01
A
g sa
lt 96
3 C
a s
alt
Pb s
alt
963
246,
272
272
M. 2
70-2
72"
Vm
CO
OC
H,
CO
OC
H,
CO
NH
,
CO
OH
CO
OC
H,,
CO
NH
,
XV
II a
M
. 164
"
vn1
M. 1
27-1
28"
VIl
I M
. 190
"
H
CO
OH
C
OO
H
M. 2
56-2
51"
XV
II a
31
2
20
CH
,CH
,CH
(CH
,),
CH
, C
OO
H
CO
Cl
CO
OH
CO
Cl
M.
223"
B.
176"
/16
359
359
N N d N
6 1 3
TA
BL
E 3
3a.
N-U
nsu
bst
itu
ted
Py
razo
le-4
, 5
(or
3)-D
icar
box
ylic
Aci
ds
and
th
eir
Fu
nct
ion
al D
eriv
ati
ves
Met
hod
s N
. R
X
X
' of
sy
nth
esis
M
.p.o
r l3
.p.
Ref
eren
ces
Der
iva
tiv
es
1H
C
OO
H
CO
OH
V
a-V
III
VI
a-V
III
VI
a-X
VII
a
XV
II a
* C
OO
CH
, C
OO
CH
, I1
a
VI
a b
Va
CO
OH
C
OO
C,H
,
CO
OC
,H,
CO
OC
,H,
Id
CO
OC
,H,
CO
NH
, V
III
CO
NH
, C
ON
H,
VII
I
CO
NH
C,H
, C
ON
HC
,H,
M. 2
44"
M. 2
60"
M. 1
41"
M. 2
63"
(d.)
M. 6
9-70
"
B. 1
80-1
85"
/2
B. 1
60-1
65"
/0.5
M. 2
48-2
50"
M. 3
27"
(d.)
M. 2
44"
863
832
243,
827
278,
635
, 408
, 83
2
1084
a
863
832
76
863
522
522
522
36
6,1
08
4
409
2 C
H,
3 C
H,O
CH
,
4 C
H,C
H,
5 C
H,C
H,C
H,
C6
H5
CO
NH
NH
, C
ON
HN
H,
VII
I
CO
OH
C
OO
H
VI
a-V
III
X a
-VII
I
CO
OC
H,
CO
OC
H,
11 a
CO
OC
H,
CO
OC
H,
IIa
CO
OC
H,
CO
OC
H,
I1 a
CO
OC
H,
CO
OC
H,
I1 a
CO
OH
C
OO
H
I1 a
-VII
I
-CH
ZC
HZ
CO
OC
H,
CO
OC
H,
CO
OC
H,
9
I H
XV
II a
I1 a
VII
I
I1 a
M.
>300
" 5
17
M. 2
29-2
30"
59
332
M.
106"
86
3
B. 1
54-1
56"/
0.00
01
863
B.
150-
152"
/0.0
5 86
3
B.
140"
/0.
005
863
M.
235"
(d.)
94,2
08,2
12,
K s
alt
552,
955
955
M.
179-
181"
86
3
Dee
. 260
" 86
3
M. 1
99"
863
* Fro
m p
yraz
ole,
K,C
O,
and
CO
, at
50
atm
., by
hea
ting
at
260"
in
pre
sen
ce o
f C
dF,
0 7-l
OY W co
d Y Y
m W 00
rd U U
m
1 r3
N r3
D W a
J
2
r"
0 (0 m
t- 4 f
0
E d d
* W
TA
BL
E 34. Pyrazole-3,4-Dicarboxylic A
cid
s an
d t
hei
r F
un
ctio
nal
Der
iva
tiv
es
N.
R
R'
X X'
Met
hod
s of
sy
nth
esis
M
.p. or
B.p
.
H
H
CO
OC
H,
CO
OH
CO
OC
H,
CH
3 C
OO
H
CH
,
CO
OC
H,
CO
OH
or
CO
OC
,H5
CO
OC
,H,
CO
OH
CO
OC
,H,
CO
OH
CO
OH
CO
OC
,H,
CO
OC
H,
I1 f
CO
OC
H,
I1 f
CO
OH
X
VII
a
VII
I
CO
OH
V
III
XIV
a
XV
II a
CO
OC
H,
I1 f
CO
OC
,H,
or
CO
OH
X
IV a
-VIE
CO
OC
,H,
VII
a
VII
I
XIV
a
CO
OH
CO
OC
,H,
CO
OH
CO
OH
C-
A
VII
I
XVII a
VII
a
VII
I
VII
I
XIV
a
XtV
a-V
III
M.234"
M. 89"
M. 97-98"
M. 247"
M. 185"
M. 51.5"
M. 265" (d
.)
M. 276"
(d.)
M. 264" (
d.)
M.158"
Ref
eren
ces
Der
iva
tiv
es
489
118,120,169
489
118
234,425
NH
: salt
226,234,982
Ag
salt
226,572,982
489
982
425
234,982
226,234,982
411
412
411
230
230
230
230
b I t-
5: I
:: N
I /
m
620
d
N LD m a m - o - N N N x N N 2 t- N * W
6 2 1
TABLE 3
4. (
can
t.)
0)
Met
hods
of
N.
R
R'
X
X'
syn
thes
is
M.p
. or
B p
. R
efer
ence
s D
eriv
ativ
es
29 0 0
CH
, C
OO
H
CO
OH
V
lll
M. 2
87"
(d.)
2
30
CO
OH
C
OO
H
VII
I M
. 285
" (d
.)
23
0
CO
OC
,H,
CO
OC
,H,
XIV
a
M.
168"
2
30
N
30
00 NHCO
CH
3 C
H,
32
H
5C
ZO
OC
~C
OO
CI
H~
HzC
,
33
a
CH
,
CH
,
CH
,
CO
OH
CO
OC
,H,
CO
OH
CO
OC
zH5
CO
OH
CO
OC
,H,
CO
OH
CO
OC
,H,
VII
I
XIV
a
VII
I
XIV
a
M. 30
2" (d.)
M. 1
41"
M. 25
0"
M. 82
"
23
0
23
0
23
5
23
5
c 6
%
CO
OC
,H,
CW
,H
,
VIl
a
M. 1
72"
16
7
35
C
OO
CH
, C
OO
CH
, X
a
M.1
36'
30
K s
alt
Ag
salt
TA
BL
E 35.
Pyrazole-4,5-Dicarboxylic
Aci
ds an
d th
eir
Fu
nct
ion
al D
eriv
ativ
es
m
N
w
N.
R
R'
X
1
CH
,
2 C
H,C
H,
3 C
,H,
'6'5
H
H
H
CH
,
CO
OH
CO
OH
CO
Cl
CO
OC
H,
,CH
,-CH
, -C
ON
' P
\C
H,-
CH
,
CO
OH
CO
OC
H,
CO
OC
H,
or
CO
NH
,
CO
OC
,H,
CO
NH
,
CO
NH
C ,H
5
CO
OH
CO
OH
CN
CO
OH
CO
OC
,H,
CN
CO
OC
,H,
CN
X'
CO
OH
CO
OH
Co
cl
CG
QC
H,
,CH
,--
C,H
2 <O
N,
,O
CH
,-CH
,
CO
OH
CO
OC
H,
CO
NH
, o
r C
OO
CH
,
CO
OC
,H,
CO
NH
,
CO
NH
C &I5
CO
OH
CN
CO
OH
CO
NH
NH
C,H
,
CN
CO
NH
C,H
,
CO
NH
NH
C 6
H5
CO
NH
NH
C,H
,
Met
ho
ds
of
syn
thes
is
XV
II a
~-
XV
II a
vm
VII
I
Id
VII
l
VlI
l
VII
I
XV
II a
VII
I
VII
I
VII
I
If
Ia
Id
I a-
VII
I
M.p
.or
B.p
. _
__
__
B.
204-
207c
'/20
M.
84"
M.
215-
216"
(d
.)
M.7
5-76
"
M.
186"
B.
168-
173"
/0.7
M. 25
3-55
" (d
.)
M.2
05-2
06"
M.1
98
-19
9"
M.
202-
203"
M.
250-
251"
M. 2
12"
(d.)
M.2
53"
M.8
8-89
"
M.1
67-1
68"
M.
147"
M. 2
07"
Ref
eren
ces
Der
ivat
ives
506
.2H
,O:
M.
233-
35
9
.H,O
: M
. 1
79
-
35
9
359
3 5"
180"
35
9
12
0,2
66
,63
5
Ag
Sal
t
12
0,2
66
B
a sa
lt
266
522
266
266
15
3,1
55
14
2,1
43
,22
6,
572,
982
15
5
Ag
sal
t
15
3
15
3,1
52
15
5
15
3
15
2,1
53
15
3,1
56
TA
BL
E 3
5. (
con
t.)
m
N
P
N.
R
R'
X
X'
Mct
hod
s of
syn
thes
is
M.p
. or
B.p
. R
efer
encc
s D
eriv
ati
ves
CN
CO
OC
H,
CO
NH
,
CN
CN
CO
OH
CO
OH
CO
OC
H:,
CO
NH
NH
C 6
H5
CO
N H
NH
C
CO
OH
CO
NH
NH
C 6
H5
CO
NH
NH
C,H
,
VII
I
XV
II a
VII
I
VII
I
vm
I a-
VII
I
VII
I
1 a-
VII
I
VII
I
I a-
VII
I
M.
190"
M. 1
97"
(d.)
M.2
17"
(d.)
M. 1
50
.5-1
51
.5"
M. 2
69"
M.
21
5-2
16
"
M. 2
08
-20
9"
M. 2
66-2
68"
M. 2
24
-22
5"
15
6
Ba s
alt
567
15
6
80
15
6
15
6
15
6
15
6
15
6
15
6
TABLE 36a.
Pyrazole-3,4,5-Tricarboxylic A
cid
s an
d t
he
ir F
un
ctio
nal
Der
ivat
ives
.n
N
UI
~-
N.
R X
X
' x
Met
ho
ds
of
syn
thes
is
M .p
. or
B .p
. R
efer
ence
s D
eriv
ativ
es
in
C
OO
H
coon
co
on
VII
I M
.213
" 2
06
,21
1,2
14
, A
g sa
lt
XV
II a
M
. 233
" 2
78
,89
1,8
94
, N
a sa
lt
297
10
57
cooc
n,
CO
OC
,H,
cooc
n,
cmc,
n,
CO
OC
H,
CO
OC
,H,
I1 a
C
Vll
l
Id
I1 a
VI
a
CO
NH
, C
ON
H,
CO
NH
, V
III
coN
nc,n
, co
ivnc
6n5
coN
nc,
W,
VII
I
CO
NH
NH
, c
oN
nN
n,
CO
NH
NH
, V
lIl
co
Nn
N.
cn
c,N
, c
oN
nN
-cn
c,n
, c
om
N=
cn
c 6n
5 V
III
-CO
NH
N
-co
Nn
N
-c
om
N
VII
l I1
II II
nc
cH
-cn
c,n
, n
cc
H-c
nc
,n,
nccn
=cnc
,n,
M.1
18
"
M.
91"
K s
alt
Hy
dra
zin
e
salt
: M. > 325"(d.)
21 1
21 1
21 1
516
.2n
,0:
M.
71-
297
214
2 97
M. >
270"
2
91
M. >
300"
29
7
297
297
297
TA
BL
E 3
6a.
(con
t.)
Met
hods
of
01
N
m N.
R X
X
' X
"
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
CO
N,
CO
N,
- C
ON
HN
HC
O-
- C
ON
HN
HC
O-
-CO
NH
NH
CO
-
--C
ON
HN
HC
O-
-CO
NH
NH
CO
-
- co
oco
-
2 C
H,C
H,C
H
(CH
,)P
C
OO
H
CO
OH
CO
OC
H,
CO
OC
H,
,CH
,-C
H,
,CH
,-C
H,
-CO
N
>O
-CO
N,
>O
k
H,-
CH
, C
H,-
CH
,
C6
H5
C
OO
H
CO
OH
CO
OC
,H,
CO
OC
,H,
-C>W
CO
OH
C
OO
H
CO
OC
,H,
CO
OC
,H,
CO
N,
CO
OH
CO
NH
C b€
i5
CO
NH
NH
,
CO
NH
N-C
HC
,H,
CO
N,
CO
OC
H,
CW
H
CO
OC
H,
,CH
,--C
H,
CH
,-C
H,
-CO
N\
>o
C W
H
CO
OC
,H,
CO
OH
CO
OC
,H,
VII
I
v I11
VIl
I
VII
I
VII
I
VII
I
VlU
VII
I
VII
I
XV
II a
Id
VII
I
XV
II a
VII
a
M.7
0"
B. 2
02"
/30
M. 1
77"
M.4
7"
M. 1
45"
M.
184"
M
213-
214"
M.7
4-7
4.5
"
M. 2
05"
(d.)
M. 7
6"
297
297
297
297
2 97
2 97
297
20
6,2
1 I
359
359
359
522
Ba
salt
22
6,5
72
,98
2
522
m,
o:
~.7
0-7
30
41
1
411
41
1
rn a,
cd > k
.2 Y
.rl
a" ill a, c) c a, k a, W
2
4
4
Q k 0
E
W
orn rn '-
2 % 3 5 5 5
X
k
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d 627
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N
m
TA
BL
E 3
7.
Dip
yraz
olyl
carb
oxyl
ie A
cid
s an
d t
hei
r F
un
ctio
nal
Der
iva
t,v
es
N.
R
R'
R"
RI
Met
hod
s of
R;
R;
syn
thes
is
1H
H
C
H,
H
H
CO
OH
2H
H
C
OO
H
H
H
CO
OH
3H
C
OO
CH
, C
OO
CH
, H
C
CO
CH
, C
OO
CH
,
4H
H
C
H,
CH
, C
H,
CO
OH
5H
C
H,
CO
OH
C
,H,
H
C,H
5
C6
H5
H
H
6
H5
H
C
OO
H
I C
,H5
H
C6
H5
C
H,
CH
, C
OO
H
CO
OC
H,
XV
II a
XV
II a
11 a
la
VI
a
XV
Il a
1 a-
VII
I
VU
I
VI
a
M.p
.or
B.p
.
M.
325"
(d
.)
M. 2
95'
(d.)
M. 1
70"
M. 2
47-2
48"
M.
273.
5-27
4"
M. 2
25-2
6"
(d.)
M.
256-
256.
5"
M.1
28-1
29"
Ref
eren
ces
Der
iva
tiv
es
4 24
4 24
86
3
200
200
962
200
200
200
Ref
eren
ces
Der
iva
tiv
es
Met
hod
s of
N.
R
R'
R
R,
R;
R;
syn
thes
is
M.p
.or
B.p
.
1 /C
OO
CH
, /C
OO
CH
, -C
C
OO
CH
, C
OO
CH
, -C
C
OO
CH
, C
OO
CH
, II
a
M. 2
20"
86
3
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OC
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CH
,
629
z
d 0
u,
4
r 0 0 U
d U
d
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d c d
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m
63 1
TA
BL
E 3
8. (c
ont.
)
0)
w
Met
hod
s of
N.
R
It'
R"
R"'
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
H
CO
OH
X
VII
a
M. 2
60-2
61"
499,
502
C6
H5
6
H5
CO
OC
H,
TI a
2
9
C6
H5
-
0B
r
H
CO
OC
H,
Ha
M
. 95"
50
2
7 -@
G
Br
H
C
OO
CH
, I1
a
M.
106-
108"
50
2
8 e
.3
eO
CH
3
H
CO
OC
H,
II
a
M. 9
2"
502
H
CO
OC
H,
II
a
M. 9
1" (
d.)
30
lo 0 0
C6
H5
C
OO
CH
, I1
a
M. 1
41"
(d.)
3
0
9 00
11
C6H
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C
OO
CH
, C
OO
CH
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a
M. 9
3"
29
A
12
C
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VC
H,
CO
OC
H,
CO
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H,
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M
. 114
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" 50
2
30
M. 1
10"
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1
3 0 0
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H,
CO
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H,
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14
C
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, C
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3
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m m m 0. 8
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v
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m 3 3
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Ern Ern u u
zrn Ern u u
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m W c Ld * 4
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2
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E
w o m m '3 8 2 5 9 5 5
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2
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V
m co m
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m
& N s
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I
m rl
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cd
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In
V
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W W 3 3 L- L-
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k=
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11
C6H
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12
dN
oz
H
HO
OY
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14
a
H
c Li
H5
V b
2 M
. 64"
V b
2-IX
6H
5
V b
2 M
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"
CH
3 vn
1 M
. 111
"
CH
3 V
b2
720
72
0
720
66
8
-H,O
: M
. 79"
B. 1
68-1
70"
/20
65
6
B. 1
62"/
15
15
O
CH
3
H
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V b
2 M
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"
65
6
B. 1
76"
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16
C
H3
CH
3 C
H3
IV a
M
. 30-
31"
51
V b
2 B
. 108
"/1
3 51
Ag
salt
Ba
salt
Eth
yl e
ster
: B
. 32
5"
Pic
rate
: M. 1
10-1
11"
17
C6H
, C
H3
CH
3 V
b2
M. 3
4"
6 84
B. 1
81"
/15
ua W
18
C
GH
5 C
H,C
H,
CH
3 V
b2
M.
92"
663
UI
TA
BL
E 4
0b.
N-U
nsu
bst
itu
ted
3 (o
r 5)
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opyr
azol
es
I H
A)
X =
C1
N.
R
R'
Met
hod
s of
sy
nth
esis
M
.p.o
r B
.p.
Ref
eren
ces
Der
ivat
ives
H
C6H
5
H
-
H
V b
2
f
V b
2
f
VII
I
V b
2
V b
2
V b
2
1' b
2
M.
115"
; 119
" 8
4,6
96
N
a sa
lt
B. 2
58"
708
*HC
1: M
. 137
"
B. 1
38"/
15
Ag
salt
M
. 142
" 79
,704
B. 2
95"
79
-HC
1: M
. 131
"
B. 1
83-1
86"
/12
M. 1
80"
704
M.
190"
27
5
B.1
15-1
16"
/0.0
01
1150
B. 1
15-1
16"
/0.0
01
1150
B.1
17-1
20"
/0.0
01
1150
8 C
H,(
CH
,),C
H,
H
9 C
H,
CH
,
V h
2
B.
132-
135"
/0.0
01
1150
V b
2 M
. 12
1.5-
122.
5"
51
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3
V a
-M
B.
251-
252"
51
14
6"/1
4
10
C
H,
gH
5
V h
2
M.
115-
116"
7
9
*HC
l: M
. 14
0-15
0"
B) X =
Br
11
CH
,
12
C
,H5
H
I11
b
M.
127-
128"
50
8
H
V d
2
M. 1
46-1
47"
81 6
VI
h 81
8
C)
X=
I
13
H
H
V
d2
M
. 72-
73"
864
a
14
CH
,
15
H
H
XIX
a M
. 15
9"
503
-(=J
Vd
2
M.
180"
61
5
16
C
H,
CH
, X
IX a
1
M.
140-
141"
50
3
TA
BL
E 4
1.
4-H
alo
py
razo
les
A) X =
C1
Met
hods
of
N.
R
R'
R"
syn
thes
is
M.p
.or
B.p
. R
efer
ence
s D
eriv
ativ
es
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4
CH
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5
CC
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H
C6
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H
H
H
n H
H n H
n
la
V c
8
VI
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a
XIX
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1 b
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a
XIX a
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IV a
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a
Ia
I11
d
v h
2
VI
b
XIX
a
M. 7
7"
B.
220"
M.6
5-66
"
B.
116-
118"
/12
M.
102"
B.
193"
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B.
167"
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M.1
19"
M.
75-7
5.5"
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504
84 7
504,
55
6,6
40
556
51
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4
54
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5 04
32
9,8
47
85
8
10
59
80
1,8
47
74
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8,9
48
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1:M
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5-17
7"
Pic
rate
: M
. 15
1.5-
152.
5"
H
H
Ia
VI
b
XM
a
vc
XIX
a
IV a
XIX
a
1V a
XIX
a
M.
145.
5-14
6.5"
84
7
84
7
51
,44
9,7
39
504
92
51
51
54
51
CH
, M
.117
.5-1
18.5
"
B.
220-
222"
M.1
08-1
10"
B.
178-
179"
.HC
1: M
. 16
0-16
4"
Pic
rate
: M
. 19
2"
'HC
I : M
. 19
6"
-HC
I: M
. 61
"
Pic
rate
:M.1
17
.5"
9H
10
CH
,
CH
,
H
gH
5
CH
,
11
CH
,
12
CH
,C,H
,
H
H
IiH
5
CH
,
B.
153-
156"
/12
B.
288"
.H
C1:
M.
115-
117"
Pic
rate
: M
. 10
1 -1
02"
-HC
I: M
. 14
5"
Pic
rate
: M
. 10
5"
13
C
H,
H
I11
d
IV a
XIX
a
IV a
XM
a
B. 1
77-1
78"
B.6
8.5"
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504
51
51
54
51
14
CH
,
15
C
H,C
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gH
5
H
C H
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B.
163-
165"
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81"
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1 :M
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"
Pic
rate
: M
. 94
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16
C
,H5
C H
C 1,
H
V
I b
M.
56"
881
B.
131-
136"
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B.
113-
115"
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51
17
CH
, IV
a
Pic
rate
: M
. 14
2-14
3.5"
; 14
6-14
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XIX
a
VII
I-X
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B.
85"/1
5 4
38
B.
112-
115"
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504
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C
H,
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OH
1
9
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CH
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OH
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CH
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a
M.
191"
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I
v1
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m"
m m l - t - t - t-
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N N N N N N 3 3 3 3 3 3
m N ,-
m N ,-
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h 3 t- W 3 3 3
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3
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m
3
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3
x
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l i
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z? ?? sq V 0 0
m N
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m
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5
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Pic
rate
: M
. 19
5-19
7"
B) X= B
r
32
H
33
n
34
H
35
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,
36
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,
39
0
.r
H
H
CH
, H
CH
,(C
H,)
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, H
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5
H
H
H
H
H
H
H
H
H
H
H
Ia
M
. 93
-94"
VI
a-V
b2
M
. 96-
97"
XIX
a
B. 2
50-2
60"
XIX
a-II
I b,
d
XIX
a
M.
76-7
7"
XIX
a B
.190
"/3
XIX
a
M.
116-
117"
XIX
a-I
11
b
XIX
a
B.76-78"/18
XIX
a M
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45"
B.
169-
170"
/20
IV
a M
. 192
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"
Ia
M
. 81
": 8
2.5"
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b, d
B
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"
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2
XM
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l
VII
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5"
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4.5"
(d
.)
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7,2
11
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51
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1
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r: M
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"
Pic
rate
: M
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8'
594
Pic
rate
: M
. 68"
88
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3
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r : M
. 18
6"
88
50
8
515
507
604, 847, 32
9.H
C1.
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/2H
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M. 1
60-7
0"
11
2
7 97
10
7
199
199
TA
BL
E 4
1. (
con
t.)
m
Met
hod
s of
N
N
. R
R
' R
" s.
ynth
esis
M
.p.
or
B.p
. R
efer
ence
s D
eriv
ati
ves
Q
H
H
42
H
C
H,
43
H
44
H
45
H
46
H
47
H
48
H
49
H
50
CH
,
CH
,
gH
5
gH
5
gH
5
gH
5
+C
Ih
gH
5
H
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a
H
la
H
XIX
a
CH
3 I1
1 a
1' c
XM
a
XIX
a-I
II a
gH
5
VI a
-XIX
a
XIX
a
gH
5
Ia
CH
, 11
1 b
M.
168-
169"
M.
90.5
-91"
M.1
17"
M.
123"
M.
93-9
6"
M.
198-
199"
M. 2
21"
M. 2
23"
M.
178"
M. 2
28"
M. 17
2"
M.
38-3
9.5"
19
9
84 7
380
10
33
504
73
9
'HC
l.AuC
1, : M
. 12
6-12
8"
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r : M
. 14
2-14
4"
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r : M
. 17
4"
76
8
Pic
rate
: M
. 19
7"
70
*H
Br : M
. 205
"
92
,95
5
42
7,5
29
427
427
427
e
427
427
51
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r : M
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5-12
6"
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0
N N - % 2 3
l 1 , b
m t- i
v) t- 4 cn i m
cd cd i
& m
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i
m
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130
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a M
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4"
130
CH
3 fi
H5
XIX
a
XM a
XM a
XM a
XIX
a
M.
116"
M. 5
8-59
"
M.
158"
M. 1
42"
M.
149"
387
80
387
571
523
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C,H
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5 fi
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C,H
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M.
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204"
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1
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a
M.
124-
125"
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5 'H
Br
80
H
H
H
V d
2 M
. 10
8.5"
56
1
XIX
21
1,5
03
81
H
CH
3 H
III
b M
.185
-187
"
73
9
-HC
PA
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l,
m
XIX
a
503
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P1/
. RC
1,
Ic1 u1
82
CH
, H
H
X
IX a
11
1.64
-65"
50
3
TA
BL
E 4
1. (
cont
.)
R
Met
hod
s of
R
' R
"
syn
thes
is _
_
83
C
H,O
H
/CH
z-C
Hz\
84
-C
HzN
C
H2
\CH
,-C
H ,/
85
g
H5
86
H
87
CH
,
88
+ nq N'
89
a
H
H
H
H
IV a
IV a
XIX
a
VC
d2
XM a
111
a-X
IX
a
V d
2
XM a
XIX
a
M.p
. or
B.p
. R
efer
ence
s D
eriv
ati
ves
M. 9
0"
50
0
M. 8
9"
50
0
M. 7
6.5
"
95
0
M.
137"
50
4
73
9
73
9
94 3
M. 6
5"
556
M. 1
96-2
02"
94
1
M. 1
35"
93
5
,2C
1: M
. 85-
88"
'2Br : M
. 78-
81"
-HC
I:M
.19
6"
.HC
l.IC
l: M
. 11
1"
-HC
I-A
uC
l, :
M. 1
74"
.HC
l.'/
. P
tC1,
: M
. 215
-220
"
TA
BL
E 4
2.
5-H
alop
yraz
o?es
-
N
~
1
2 3 4 5 6 7
m
51
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I
A)
X =
C1
Met
ho
ds
of
R
R'
R"
sy
nth
esis
M
.p.o
r B
.p.
Ref
eren
ces
Der
ivat
ives
C6
H5
H
a
H
HO
OC
CH
3 C
6H
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CH
,CH
3 C
H3
CH
,CO
OH
C
H3
111
b
V b
2
V b
2
VII
I
IVa
V b
2
IVa
V b
2
IV a
IVa
B. 2
50"
Oil
M.
125"
B. 1
57-1
58"
M.
62"
B.
296-
297"
M.
167"
M.
19
gC
674
674
667
667
84
,95
,88
3
84
79
,68
3
683
84
713
.HC
10
4:M
.14
8-1
49
"
. HC
1: M
. 95
"
. HC
1.l/z
PtC
1,.
H,O
: M
. 19
3"
. HC
IO, : M
. 99"
Ag
salt
Ba
salt
Na
salt
NH
4+ s
alt
Eth
yle
ster
& t- 3
N P
? c
m m m
II m % $ V v v
3 N 3 3
0 i
2 V
$ 2 v v
Ln 3 m e 3 3
b t- I
m 0 3
i
x x x m x x X m m X z
3 N - 0 3 N m 3 t-
3 W 3
W N
v) N
m q N N N N
649
i t -
w t - c a d t-
3 L-
m X
0 m rn N
650
W L- 3
s W P- i
3 3 3 U Y m U Y
W 3
W (D
3
Fd
z7
d
V
V
z7
5
V
m 3 P-
b L-
UY P- I
s
Ei k-
d
D?
V
u
m 3 P-
i N i
i
l?
D? V
m 31 V
W * i u a * * 0 *
65 1
t- W W 2 : : c - t -
N n * b * N N Q P
W e e m * *
m ^ m e m o ) o ) L - L - 3 L- * 3 w w t- iD w t -
w m o 1 % e * m
652
653
TABLE 4
4.
3,4-
Dih
alop
yraz
oles
N.
R
1
2 3
4 5 6 7 8 9 10
11
12
13
14
H
H
H
H
H
H
H
H
H
H
'6*5
CH
3
CH
3
CH
,CH
,
R'
H
H
CH
3
CC
l,
CH
3
CH
3
CH
3
C6
H5
C6
H5
GN
o2
X
Br
I c1
c1
c1
c1
Br
c1
c1
c1
Br
c1
Br
c1
X' -
Br
I c1
c1
Br
I Br
c1
Br
Br
Br
Br
Br
Br
Met
ho
ds
of
syn
thes
is
XIX
a
vc
WC
a
* XIX
a-V
III
XIX
a
XIX
a
XIX
a
XIX
a
XIX
a
VII
I
XIX
a
XIX
a
XIX
a
WC
a
XIX
a
M.p
. or B
.p.
M.1
33
.5"
M. 1
62-1
63"
M.
115-
117"
M.
12
8"
M.
166-
167"
M.
140"
M. 1
52"
M.
145"
M. 9
5-96
"
M. 9
0"
M.
130"
M.
83.5
-84"
M.
56"
M.
74"
M. 3
9"
Ref
eren
ces
Der
ivat
ives
508
50
3
50
4,6
96
765
504
696
696
508
704
704
Ben
zoyl
der
iv : M
. 70
"
Ben
zene
sulf
onyl
der
iv : M
. 12
6-12
7"
. Br,
: M
. 18
6"
704
10
8,9
50
88
3
525
88
3
15
CH
,C,H
, C
H3
C1
Br
XIX
a
M. 62-63"
84
B. 195"/13
16
C,H
, C
H3
C1
C1
V b
2-X
IXa
Oil
654
17
C,H
, C
H3
C1
Br
XM
a
M. 194"/15
654
* Fro
m 3-methyl-5-chloropyrazole w
ith
dil
. HN
O,
TA
BL
E 45.
3,5-
Dih
alop
yraz
oles
X' N
'
Met
ho
ds
of
N.
R
R'
X
X'
syn
thes
is
M.p
.or
B.p
. R
efer
ence
s D
eriv
ativ
es
0,
cn
cn
1H
H
B
r
Br
I11
c M
. 151"
506
2H
'C
jH5
Br
B
r
Vfl
M. 157-157.5"
389
3 C
,H,
H
c1
c
1
V b
2 M
. 25-26"
706
B. 170-172"/16
4 C
,H,
H
Br
Br
Vb
2
M. 5
0"
674
5 C
,H,
CH
, c
1
c1
V
b2
B. 155"/16
706
6 C
,H,
CH
,CH
, C
1 c1
V
b2
M. 81"
71 1
3 - w c o r r m w w
d p x
E a s l
8
8
X
w m
W n I
m n
r'
d
8 8
m L
z7 V
g 0
m m 3
ln t- I
w t-
i
3 w
k-
L F9
h m
D? V
2 V
w
N
N O I C O N F J r m o t - w m t -
B
B
D? V
u)
xu V
3 3
656
3 m m
N 3
-a H
a a
N a X V
Fx V
m
c o o 3 a m W W W - t-t- m r m m m W W m a n m m
c- (D
m t- W
m t- (D
N d r dr 0 3 3 t - l - t-
N m
s
3 CI] 0 N m 3 m 3 t- 3 n d r m W
3 3 3 3 N 3
6 5 7
m c
c .3 Y
.3
a"
8
2
m u
W * 19 m n
19 m m
10 m m 3
W m i
m m
m
L- 3 L-
b u3
2
t- 3 t- t- 3 L-
L - t - M M c - t -
658
TA
BL
E 4
7.
3,4
,5-T
rih
alo
py
razo
les
N.
R
X
X'
X"
1H
B
r B
r
2H
I
I
3 C6H5
C1
c1
4 C6H5
C1
Br
5 C,H5
Br
Br
Br
I c1
c1
Br
-
TA
BL
E 4
8.
Hal
odi-
an
d t
rip
yraz
olyl
s
N.
Com
pou
nd
s
Met
hod
s of
sy
nth
esis
M
.p.o
r B
.p.
Ref
eren
ces
Der
ivat
ives
V b2,
i, X
IX a
M
. 180
-181
"
474
XIX
a
M. 1
84"
50
8
XIX
a
M. 2
21"
50
8
XIX
a
M. 8
2"
674
XIX
a
M. 8
5"
674
XIX
a
M. 1
06-1
07"
1
08
,67
4
M. 12
2"
-
Met
hod
s of
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
m
UI
W
V b2
M.1
66
-16
7"
9
62
XIX
a M
. 159
-160
"
377
L- L- m
m t- N
N r- N
I
5
d
8
k % n u
t- t- m
d
m 0 L-
u !5
3 Ln 3
s
N m N
s
*
50
660
m
2 M
$
H
V
c R
.3 fi
B .- a
u 8 Y
fi m 3
N
2 6
l d m
w *
3 E
m 0 LD n 3 t-
m - t-
h
a I
W LD 3
I z
i % zi
& 3 (D 3
b W 3
rd d d
2 @ t?
I h m
3 N m
m s
rd
t?
E uhL 3 . 2
*
m 3
n s N
h
a v
t- 0 N
N N 3
i zi
d of
@ t?
3
3- i-: L 0
m N *
20 3 3
L- 3 3
I
z!
n s
66 1
TA
BL
E 4
9h.
Hal
opyr
azol
es:
Pyr
azol
ium
Sal
ts
X= B
r
N.
R
R'
R"
R"'
Y-
Met
hods
of
syn
thes
is
M.p
.or
B.p
. R
ePer
ence
s D
eriv
ativ
es
1H
2 C
H,
H
CH
, H
B
r XIX
a
M. 1
26"
508
CH
3 C
H,
CH
, B
r X
IX a
50
8
1) x
= c
1
N.
R
R
R"
R"'
Y-
Met
hods
of
syn
thes
is
M.p
.or
B.p
. R
efer
ence
s D
eriv
ativ
es
1 C
H,
CH
3
CH
, H
I
IV c
M
.219
-22I
0(d
.)
51
Pic
rate
:M.
129.
5-13
0.5"
2 C
H,C
,H,
-3
CH
, H
I
3 C
H,C
,H,
CH
3 H
C
H3
I
4 C
H,
CH
3 C
H,
IV c
M
. 129
-130
" 51
IV c
M
.159
"
51
I IV
c
M. 1
96"
51
M. 1
27.5
-128
"
2) X
= B
I
'GH
S C
H3
H
CH
3 I
Nc
M
. 206
" 88
8
1) x
= c1
Met
hod
s of
sy
nth
esis
M
.p.o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
N.
R
R'
R"
Y
Nc
M
. 172
"; 1
61"
(d.)
6
74
,68
0
M. 1
47"
M. 2
07"
I c1 . C1.
PtC
l,.H
,O
CH
,CH
3 H
H
do
, I
M. 2
09"
674
M. 1
81"
M.2
17"
M.l
56
"(d
.)
674
M. 2
35-2
36"
84
,69
6
M. 2
43-2
47"
M. -
240"
M. 2
52"
84
M. 1
36"
84
,69
6
Nc
c1
. C1.
'/z P
tC1,
I I
C6
H5
4 C
H,
CH
,CH
,CH
, H
H
CH
3
CH
, H
IV c
Nc
Nc
V b
2
Br
C1
C1.
HgC
l,
c1. '/
z M
Clq
. H
20
: M
. 243
"
M.1
32"
5 C
H,
CsH
B
H
Nc
V b
2
M. 1
67"
M. 1
30"
M. 1
36"
683
683
.4I:
M. 1
05"
. 2H
,O:
M. 1
0"
I C1
C1.
HgC
1,
Cl.
l/,
RC
l,
. H,O
: M
. 214
"
TABLE 49b.
(con
t.)
Met
hod
s of
m
m
P
N
. R
R
' R
" R
"'
Y-
syn
thes
is
M.p
. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
6 C
H,
CH
,CH
, C
H,
H
7 C
H,C
H,
CH
, C
H,
H
8 C
H,C
OO
H
CH
, C
H,
H
CH
,CO
OC
,H,
9 C
H,
CH
2C
6H
5
CH
, H
10
CH
, C
6H
5
CH
, H
11
CH
,
12
CH
,
13
C
H,
14
CH
,
<f'
CH
, H
C6
H5
O,N
o{-k
No.
0
9
I c1
0,
c10
,
I I I I c1
Br
I c1. b
MC
1,
I I I C1
c1.
PtC
l,
I
IV c
IV c
IV c
V b
2
VII
I
IV c
IV c
IV
C
Nc
Nc
VlI
I
IV c
M. 150"
M. 184-186"
M. 208-213"
M.
187-
188"
M. 191-194a
M. 156"
M. 1
30"
M. 1
60"
(d.)
Dec
. 120-175"
Dec
. 197-200"
Dec
. 177"
M. 2
18"
M. 207"
M. 196.5"
M. 138"
M. 145"(d.)
M. 288"
M. 169"
84
84
713
113
51,8
4
654.983
654
654
654
716
716
720
720
120
u = v u
2 2 2 2 0 v u u 2 2 2 2
m m m
d d Ern v u u
L1
d r" 4 u u v
L o w l - - 3 3
a x
d x" u u
d s " v LU
m m - 3
T T r n T
0 - N O N " N
665
TA
BL
E 4
9b.
(con
t.)
m
Met
hods
of
m
m
N.
R
R'
R"
R
"'
Y-
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
24
C
,H,
CH
, C
,H,
H
c1
I c1
. lb
PIC
lq
26
C,H
, 'S
H5
CH
, H
30
CH
,CH
, C
H,C
H,
31
CH
,CH
,CO
OH
C
H3
CH
2CH
2CO
OC
,H,
CH
, H
CH
, H
CH
, H
CH
, H
CH
, n
I3r
1 I I c1
VII
I M
. 194
"
721
Nc
M
. 172
"
72
1
M.2
22"
Nc
M
. 17
2"
721
V b
2 M
. 105
" 53
6
VII
I M
. 110
"
687
IV c
M
.231
-232
"
V b
2
IV c
IV
C
IV c
Nc
IV c
IV c
IV c
M. 2
32"
M. 23
4"
M. 24
5"
M. 1
53"
M. 2
64"
M.2
25"
(d.)
M.1
87-1
91"
M. 1
42"
M. 13
6"
M. 13
8"
71 7
717
717
71 7
88
3
84
,69
6
713
713
661
33
CH
,C,H
,
34
CH
3
35
C
H,
36
CH
,
37
C,H
,
38
C,H
,
39
C,H
,
40
C,H
5
H3
C
41
23
H
I
CH
3
I O2N
-NO,
/ 0
9
I c1
c1
I C1
.h P
tC14
c1
Br
I c1
I c1
I c1.
RC
1,
C1.
HC
I. P
tC14
I
IV c
Nc
Nc
V b
2
VII
I
IV c
Nc
Nc
Nc
VII
I
IV c
VII
I
Nc
IVC
M. 20
0-21
6"
M.
184-
188"
(d.)
M. 12
4"
M. 1
65"
M.9
4"
M. 23
5"
M.1
62"
M.
197"
M. 1
76"
M. 14
8"
M. 16
7"
M. 2
13"
111.
203"
M. 23
6"
M.
187"
84
51
51
685
719
719
719
719
719
719
71 9
703
703
667
c1
vni
M.-
214"
67
8
Dr
Nc
M
,218
O(d
.)
678
.2B
r: M
. 146
"
V b
2 67
8
I IV
c
M. 2
33"
678
.41:
M.5
7"
TA
BL
E 4
9b.
(con
t.)
m
m
N.
R
R'
R"
R"'
Y-
Met
ho
ds
of
syn
the
sis
M.p
. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
43
-3
CII
, H
I
M.
259"
71
4
44
C,H
, C
H2C
H:C
H2
CH
, H
C
1 V
III
M.1
82"
648
Br
Nc
M
.196
" 64
8
45
C
,H,
CH
3
CH
, C
H,
Br
IV c
M
. 23
0"
719
3)
X=
I
46
CH
,
47
o
m2
48
C
6H
6
49
C
,H,
50
C
6H
5
52
CH
,
63
C
H,
54
C,H
,
CH
3
CH
3
CH
,CH
,
CH
,CH
,CH
,
CH
2CH
=C
H2
CH
2C
H3
C6
H5
C6
H5
CH
2C
H3
CH
3
C,H
, H
CH
, H
CH
, H
CH
, H
CH
, H
CH
, H
CH
3
CH
,
CH
, C
H2
CH
3
CH
3
CH
,
CH
, C
H,
I I c1
I I c1
I I I 1
c1
I I
TV c
-V
c8
IV C
-V c
8
VII
I
N c
-V
c8
IV C
-V c
8
VII
I
N C
-V
c8
N c
-V c8
IV C
-V
c8
N c
-v c
8
VII
l
N c
-V
c8
IV C
-V c
8
M.
188-
190"
79
M.
229"
67
8
M.2
22
"(d
.)
702
M.
240"
(d.)
I0
2
M.
225-
226"
5
3
648
M.
195-
194"
M.
203"
(d.
) 64
M.
231"
7
11
M.2
17"
684
M.
196"
6
63
M. 1
90"
719
M.2
22-2
23"(
d.)
719
719
N.
R
R'
Met
hod
s of
R
efer
ence
s D
eriv
ativ
es
R"
R'"
R
""
Y-
syn
thes
is
M.p
.or
B.p
.
C6
H5
C
H3
C1
H
c1
c
1
V b
2
1 N
c
2 C
H3
CH
3 C
H3
Br
c1
B
r N
C
3 t
>B
r
CH
3 C
H3
C1
c1
I
Nc
'CsH
5 C
H3
CH
, B
r c1
I
IV c
'bH
5
CH
3 C
H3
I c
1
C6
H5
C
H3
C1
Br
c1
I I
IV c
-v c
8
SO,C
H,
IV
c
M.
155-
158"
M. 1
66-1
67"
M. 1
99-2
03"
M. 2
30"
M. 2
29"
(d.)
M.
178"
M. 2
10"
692
692
84
714
645
702
692
692
m
-2 0
TA
BL
E 5
0.
N-N
itro
pyr
azol
es
N.
R
R'
R"
Met
hod
s of
sy
nth
esis
M
.p.
or B
.p.
Ref
eren
ces
Der
ivat
ives
1H
H
H
X
IXb
M
. 93"
49
6
C6
H5
H
H
3 C
H,
H
CH
,
XM b
M. 1
22"
310
XIX
b
M. 6
6-67
" 49
6
4 C
HzC
H3
H
CH
zCH
3 X
Mb
O
il
496
5 C
H,
CH
3 C
H3
XIX
b
496
TA
BL
E 5
1.
3-N
itro
pyra
zole
s
R" H
'lrrN
oZ
N/N I
N.
R
R'
R"
Met
hods
of
syn
thes
is
M.p
. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
1H
C
6H
5
H
2H
H
3H
H
+I
I1 c
M
. 209
-210
" 81
8
V d
l 81
6
VI
b
818
* M
. 27
2-27
4"
436,
615
534
~H
,CH
,OH
C6
H5
H
H
I1
1 d
M. 9
7"
ul
C6
H5
4
cL
6 C
6H5
H
CH
, X
IVa
M
. 96"
H
CH
,CH
, X
IVa
M. 78"
1133
422
422
422
HC
1: M
. 30
0"
CH
31 : M
. 25
7" (d.)
. CH
,C1
: M. 2
90"
(d.)
. CH
,OH
: M
. 28
7" (
d.)
Pic
rate
: M
. 21
2"
* Fro
m n
icot
ine
wit
h HNO,
n Y
X
m
m
3
x x x 31 X 31
m X Z x X X
N m e m W t-
673
TA
BL
E 5
2a. (
cont
.)
m 2 N.
R
R'
R "
Met
hod
s of
sy
nth
esis
M
.p.
or B
.p.
Ref
eren
ces
Der
iva
tiv
es
1133
8 9 10
11
12
13
14
15
16
17
18
H
a c1-
+-\
CH
~C
OC
H,
1133
H
1133
H
1133
H
IV a
IV a
M. 9
9.5"
M. 5
6"
500
500
CH
,OH
CH
,N(C
H&
H
H
M.
85"
500
IV
a
H
1042
38
1,4
62
,47
5
312
IV a
Ia
XIX
b
M.
132-
135"
M. 1
26-1
27"
M. 1
29-1
30"
H
H
CH
,CH
,CO
OH
'IjH
5
H
H
312,
381
312.
381
Ia
XIX
b
M.
148"
M. 1
51-1
52.5
"
H
M. 1
55-1
56"
38
1
381
381
Ia
v1n
XIX
b
H
& m 3 I
3 i
7 m f
S $ w
s s P P
X
X
x m X m X
X 5:
m X
X U
v ) ( D N N d N m
N N
Q, 3 : : F : N
675
N m n N m m
cu m m P
* m N
n m 3 - m m
m P 3
N t-
i
d
h
z
4 u m
E u
676
D 7 0
Lt? u
ZY V
Lt? V
N q 0 3 q *
b m 4
I *
b S N O " 3
A C : m " N O " i
i i i
n
d
z
iQ * m *
2 V
d
5 g g
2 v
D? v
t- * m *
m m ma-
N
t- m
bo4 t - m I I t - c o
i"
w 3 4 3
ii
n
1 F
B
9
D? V
j cn * 0 3
m m
677
0 0 m
0 3 3 3 I 2 3
A
Ld
k
h 0
3
0 0 m
0 N CO
i
d
2
h 0
N
3 m
0 3 r- r(
CO CD 3
I
i
0
2
I 3
m
w w N N * *
P x u ,R
w
TA
BL
E 5
3.
1,4
-Din
itro
py
razo
les
OJ
-3 W
N.
R
R'
Met
ho
ds
of
syn
thes
is
M.p
.or
B.p
. R
efer
ence
s D
eriv
ativ
es
1
CH
, H
X
IXb
M
. 48"
M. 9
1-91
.5"
2 C
H,
CH
, X
IX b
496
496
TA
BL
E 5
4.
3,4
-Din
itro
py
razo
les
Met
ho
ds
of
N.
R
R'
syn
thes
is
M.p
.or
B.p
. R
efer
ence
s D
eriv
ativ
es
__
__
__
__
_
~_
_
0
1H
X
IX b
61
6
1133
,HC
k M
. 13
0"
680
0 i m m
68 1
TABLE 55. (c
ont.
)
m
Met
hods
of
Ref
eren
ces
Der
iva
tiv
es
N.
R
R'
R"
sy
nth
esis
M
.p. o
r B
.p.
03
24
25
26
21
28
29
30
31
32
33
34
35
C6
H5
l
Ia
Ia
Ia
Ia
Ia
Ia
Ia
la
Ia
M
. 137.5"
Ia
M
. 130"
Ia
M. 135"
M. 153-154"
M. 100'
Oil
M. 109. 5"
Dec
. 170"
Oil
M. 92-93"
M. 165"(d.)
M. 88-89"
910,1053
910
910
1144
1080,1141
1129
910
642,1129
1129
642,1129
642,1129
642,1129
3 t- m
m W 3
z!
V
In
3 u
< u
In
% u
W m
683
t- W i (D
3 3 -
m - 0 t-"
m m m N W m
3
5: 3 W
Ln 0 In
3 o i L n ( 0 ln W
m t- i
t- t- i
I
s
m m w m
6 6 6 6
o m m x u v 8 8
O n 2 B x x
8 8 8 8 v u U U
0 x x x x u x x x x x x
m x x x x x m
2" U x
N
m m
( 1 - r w t - m
684
13
14
15
16
17
18
19
20
21
22
23
24
25
26
g 23
UI
28
CH
, H
C
6H
5
CH
,CH
, H
C
H,C
H,
C6
H5
H
C
H,
C6
H5
H
c6
H5
CH
, C
H,
H
H
-CH
~C
H(C
H,)
CH
~C
H~
-
-CH
ZC
HZ
N<&
CH
3 --
CH
,CH
,CH
,CH
,
-CH
2CH
2CH
2CH
2-
H
H
H
H
CH
,(C
H,)
&H
, H
H
H
H
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,Cl
CO
CH
,Cl
CO
CH
,Cl
CO
CH
,Cl
m c
XX
Ve
XX
V e
-n
XX
V e
-VIl
I
Ia
XX
Ve
XVm
b
XX
Ve
XX
Ve
XX
Ve
We
XX
Ve
XX
V e
-VII
I
XX
Ve
XX
Ve
XX
Ve
XX
Ve
XX
Ye
B. 8
8-89
"/4
0
B. 8
4"/2
3
B.
70"/
12
M. 6
8"
M. 1
60-1
61"
M. 4
5.5
-46
.5"
B.9
4O/1
2
M.4
3"
B.1
58-1
60"
M. 87"
B.
226"
/10
M. 88
'
B. 1
90"
B. 1
43"/
17
M. 8
2.5
-83
.5"
M.
154-
155"
B.1
30"
/15
B.
170-
172"
/52
M, 3
3-34
"
B. 1
40-1
45"
/0.0
2
M. 6
7.5-
68"
M. 15
5"
947
61
,72
6,9
67
505
505
67
501
67
955
1036
523
61
74
96
9 57
725
1148
726
598
TA
BL
E 5
6a.
(co
nt.
)
a
m
X
m
N.
R
R'
R"
Met
ho
ds
of
syn
thes
is
M.p
. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
29
CH
,
30
CH
,
31
CH
,
32
CH
,
33
CH
3
34
H
35
H
36
C
H,
37
CH
,
38
C
,H,
39
CH
,
40
CH
,
41
CH
,
42
CH
,
43
C
H,
44
CH
3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
CO
CIi
,SH
CO
CI1
20C
GH
s
CO
CH
,NH
,
CO
CH
,NH
CH
,
--C
OC
H,N
HS
Oz~
'> ,-
CH
?
CO
CO
OC
,H,
CO
CH
,CH
,
CO
CH
,CH
3
CO
CH
2CH
3
CO
CH
zCH
j
CO
CH
,CN
CO
CH
,CN
--C
OF
IIC
H3
la
la
VII
I
VII
I
Ia
XX
VC
XX
Ve
la
XX
VC
la
XW
II b
XX
Ve
Ia
la
la
Ia
me
Ia
M.
118-
119.
5°
M. 8
5-87
"
M.
101-
102"
M. 9
5"
M.
112-
113"
B.
155-
156"
/16
B. 1
48-1
50"/
48
B.9
9-99
.5"/
24
B.9
4"/1
2
M. 33
-34"
111.
77-7
8.5"
M.
118-
121"
M.1
53-1
54"
M.
144.
5-14
5.5"
111.
143.
5-14
4.5"
B.
126-
128°
/40
M.
34-3
5.5"
87
6
878
726
726
87
7
72 5
725
363
726
67
67
67
875
872
877
877
726
67
.2H
C1:
M
. 13
4-13
5"
Pic
rate
: M
. 15
1"
Pic
rate
: M
. 10
0"
Pic
rate
.HC
1: M
. 24
0"
.HC
lO.,:
M
. 51
"
-BIO
,: M. 15
7-15
8"(d
.)
c - m m m m m C t - C c W
m N Lo
m N in
in m 7. - 0 i i
m m N in LD
03 0 m 7. 0)
i i e
ci a m a I - e I
d m o N C i n m
s " $ $ U U U
s" U
r 9 r a
c1 9 51 a d d U 0 U U U
B U
X s E r n 3: r
(1 t- m
i
m d d d d d
F m
Z F L ? z a m 0 t - t - t - t- t-
m m m m m m m i~ i~
m 0 c m
N 0
I m rn 3
2
m 2.2: m m s m m
0 m V u u u u u
m o d
0
am U
l? U
1;" d d d
W N * (0 i?
ln L o r n iD (0 L D i D ( D t - m
688
d
m F
a i
d W N W z
m
d
m N F m t- m c W
(D co
i i i i
d
F co
3 W
i
d V
ln W
2" V
d
W c- W 0
m X 2" 2"
V V V
z m X 51
2" 2"
F c-
U U U d u d
- 01 W m W
m X V
N c
689
TA
BL
E 5
6a. (
cont
.)
Met
hod
s of
0,
(D
R
R'
R"
X
sy
nth
esis
M
.p. o
r 9
.p.
Ref
eren
ces
Der
ivat
ives
0 N.
74
H
75
CH
3 H
C
H3
76
CH
3
77
CH
3
78
H
H
CH
3
H
-3
H
H
79
-3
H
H
80
CH
,(C
H,)
,CH
, H
H
81
CH
,(C
H,)
,CH
~
H
H
82
CH
,(C
H&
H,
H
H
XX
Ve
M. 8
1"
870
a
XX
V e
l 87
0 a
Ia
M
. 129
-132
"
870
a
XX
V e
87
0 a
XXV e
l 87
0 a
CO
C,H
,
CO
CsH
5
CO
C,H
,
CO
C,H
,
Ia
M
. 75"
XX
Ve
Ia
M
. 73
"
870
a
870
a
8'10
a
483,
55
6,7
24
m
e
M.
46"
B.2
81"
B. 2
20-2
25"
/60
B.1
40"
/11
me
B
. 155
-157
'/14
65
XX
Ve
B
. 17
4"/2
.5
534
9. 1
35-1
37°/
0.
001
1148
B. 1
40-1
45"
/0.0
02
1148
XIN
e
XX
Ve
.HC
10,:
M
.161
-162
"
83
C
H,(
CH
~)~
~C
H,
H
H
84
C6
H5
H
H
CO
C,H
,
CO
C,H
,
XX
Ve
XX
V e
B. 144
-146
~m.0
01
1148
M. 57-59"
212,955
M. 64-65"
B. 20
0-20
2'/5
94
7
B. 1
58"/
2 442,126
M. 88-89"
67
M. 83-84"
67
67
67
Pic
rate
: M
. 160"
CO
C,H
, 85
C
H3
H
CH
3 l
a
XX
Ve
la
Ia
VII
I
XX
V e
86
CH
3
87
C6
H5
CO
C,H
,
CO
C,H
,
H
H
CH
.3
88
H
~ C
H,C
H,C
H,C
H,
CO
C,H
,
CO
C,H
,
XX
V e
M. 58.5-60
48
B. 208-210"/13
B.
20
ZY
12
48
48
89
H
-CH
,CH
,CH
,CH
(CH
&
XV
III
b
XX
V e
Q
-CH
2C
N*
XX
Ve
96
90
H
C
OC
,H,
M.141"
Oil
91
-CH
(CH
,)C
H,C
H,C
H,
~ H
C
OC
,H,
Ia
48
873
813
92
C
H3
H
CH
, l
a
XXV e
d
H
-co [)
93
H
H
CH
3 I
a
M.1
30"
67
94
H
H
'6"5
I
a
M.151-152"
67
m
+-
95
In -c
o (3
H
CH
3 H
I1
1 b
B. 95
"/13
60
O h w w h tn
Q
B
n xw
h m
h 0 W 0 0 w 0
0
: : s
n
9 2" E U 0 V d
U X X X B
n
2 xw X U U
3 0 0 z 3 m m m m
2" u x
B U
N m - 2 a a
& 3 3 4
& 3 3
i
& I m CC
i
P Ln
3 Ln
I
i
n h CC
N Ln -r 3 0
3 3 3 3 e 0 3
3 3 3 3 3
h m * 0 o m S P 3 i O S
6 93
c W
&
m
t- I t-
i
d 3
3 4 7
% U
X
Xm U
0 N 3
c W
P
i m W
Q
E
a?
rn 0 0 2 E t - t- W m m
0 0 i
I N
3
N
i n 0
i i
w W
G d V
X
B V d
U
d N 3 rn N 3
W '0,
W m m
m m i s 2 2 m m
W
c1 m N
m
m N 3
i W m - i
W
2 6 o w a,
m " X
L9 7% 0
Y
(c
m V
m
U
m
3: c? a X'
U
m
6 V
i m c
m
m s: ie, m 21 m
z W N c
m
:: m
t- N " Ln
N - 695
w In 0 3
0 In
W I
m
W
&
mi
z;
Q,
k mm 8 u
I
m
mm u D? u
3 cu
In E- m
696
P
d d d 0 2
s :: x z x
4 x x u x
u?
x 8 L
0 a
c1 CI w Y w
m m
In W
697
Y 3
rn
2"
m t- 'a
& 0 3 I
m m
z;
V
G
m
u u mm
8 v
m
m
m
m W i
ln I
m w m m w w 3 - m
3 m 3
s
d V d Y C U Y
?!! 8 u
m
r d d w w w w m m
3
t- &
ln I
0 t- rl
i
P C
= 5 b - x
In
?!:
8 8 8 u u 5
m 5 m
0 3
3 rn m 3 3 3
* * *
p* 3
15
H
H
-c
o%
p)-
c,
I1 c
M
. 12
9-13
1"
M.
159"
M.
187-
187.
5"
580
16
H
I11
d 58
4
H
17
H
II
C
580
H
-c,ocH
3
H
18
H
I
IC
M
. 97-
97.5
"
M.
134.
5-13
5"
M. >
300°
580
19
H
20
H
I1 c
58
0
-CH
=CH
CO
CC
&
XV
II b
-VII
I
XX
IV b
XV
II b
-VII
I
375
410
21
H
22
H
23
H
-C(S
O~H
)=C
HC
OC
O-
- C
(NH
C,H
,)=
CH
CO
CO
-
- cc
l=cc
lcoc
o-
375
Na
salt
M.
360"
(d.)
V
III
XV
II b
-VII
I
XX
IV b
VII
I
375
408
408
408
24
H
25
H
- C
(NH
C~
H~
)=C
C~
CO
CO
-
-CH
=CH
C[C
H(C
H,)
,]=C
HC
O-
M. >
300"
M. 1
04-1
05"
I
a
VII
I
635
Br:
M. 1
61-1
62"
635
635
m
26
H
W
(D
Ia
M
. 21
6-21
7"
TA
BL
E 5
7. (
con
t.)
4 0
* N
. R
R
' X
M
eth
ods
of
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
27
C/H=CH
COOH
Q coco
-
***
635
XVII b
-VII
I 27
7 E
thyl
este
r
Met
hyl
este
r:
M. 290-292"
* ** F
rom
3-b
enzo
yl-4
-dia
zo-
5-p
hen
yl-p
yraz
ole or 3 -b
enzo
yl- 4
-ph
enyl
- 5-
dia
zo-p
yraz
ole
by
irra
dia
tion
in
ben
zen
e.
***
Fro
m 5-bromo-6-isopropyl-1,2-diazoazulene b
y tr
eatm
ent
wit
h h
ot a
lkal
i.
Fro
m 0
-dia
zoac
etop
hen
one
by
trea
tmen
t w
ith
NaO
H i
n d
ioxa
ne
at 85", o
r w
ith
NaO
CH
,.
TABLE 5
8.
3-A
cylp
yraz
oles
Met
hod
s of
N.
R
R' R"
X
syn
thes
is
M. p
. or
B. p
. R
efer
ence
s D
eriv
ativ
es
2 C
6H
5
H
CH
,
3 C
6H5
H
H
4 't
jH5
H
CH
,
6 C
6H
5
H
C6
H5
-l
0
-7
C
H,
CH
, H
CH
O
xmn
g M
. 56"
88
7 O
xim
e: M
. 17
7-17
8'
CH
O
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
B. 1
15-1
2071
3 S
emic
arb
azon
e:
M. 2
01"
G
uan
ylh
ydra
zon
e:
HN
0,:M
. 20
0"
I1 f
B-1
85"/
22
489
Dip
rop
yl a
ceta
l
888
Oxi
nie
: M
. 16
6"
Id
Ph
enyl
hyd
razo
ne:
M
. 17
3"
Sem
icar
baz
one:
M
. 183
"
Gua
ny!h
ydra
zone
: H
NO
, M
. 15
5"
335
Ph
enyl
hyd
razo
ne:
M
. 182
"
XIV
c
M. 90"
24
4,2
45
, O
xim
e: M
. 17
5"
* 90
9 M
. 56
" 2
46
O
xirn
e-b
enzo
ate:
Sem
icar
baz
one:
M
. 228
"
XIV
b
M.
134-
135"
35
5
XIV
a
M. 8
8"
171
In d
M
. 19-
20"
19
8
B. 6
3.5
-65
"/0
.1
a m
I I m
m 3 W - - W 3 (D
3
X X
m 3
N 3
0 0 a m 3 3
702
Ln 3 * -
zm m o m
( D o c - m 3 3 3
19
C,H
,
20
C
,H,
H
CH
3
'gH
S
'CiH
5
CO
C,H
,
CO
C,H
s
***
M. 9
1"
XX
VI
el
M.
155"
909
Oxi
me:
M. 1
54"
2,4
- din
itro
ph
enyl
- h
ydra
zon
e: M
. 21
0"
184
2,4-
din
itro
ph
enyl
h
ydra
zon
e:
M.
210-
212"
Othe
r 3-
acyl
pyr
azol
es
N.
Com
pou
nd
s M
eth
ods
of
syn
thes
is
M. p
. or
B. p
. R
efer
ence
s D
eriv
ativ
es
22
n5c:3
3cH0
H
5
6
Ia
M
. 138
"
34 8
I1 a
M
. 76
"(d.
) 49
9
***
Fro
m d
iazo
met
han
e an
d a-phenylazobenzoylacetone.
4
0
w
4
0
P
TA
BL
E 59.
4-A
cylp
yra
zole
s
H"
N.
R
R'
R"
~ ~~
~ -
1
CA,
H
I1
2 C
,H,
H
H
3 -
0L
l
H
H
4 O
OC
%
H
H
CH
O
CH
O
CH
O
CH
O
CH
O
CH
O
CH
O
XXV e
2 B. 1
06-1
08"
/20
383
2,4
-din
itro
ph
eny
l h
ydra
zon
e:M
. 264
-65"
mli
: 16
7. 5
" O
xim
e:M
{ sp: 1
35"
V
IE
M. 8
5-
3 80
XX
V e
2
an
ti: 99"
0-A
cety
l0xi
rne:
M { s
vn:
103"
A
ni1
:M. 1
20-1
21"
u-B
rom
odn
il:
M. 1
02'
m-B
rorn
onil
: M. 12
6"
y-B
rom
oa
nil
: M
. 169
"
Dim
eth
ylim
mon
ium
d
eriv
ati
ves
: -c
hlo
rid
e: M
. 85
-86"
-c
hlo
rop
lati
nat
e:
M. 2
28"
XX
V e
2
M. 1
18"
10
83
XXV e
2 M
. 94"
10
83
XX
V e
2
M.
1 80°
3
84
XX
V e
2 M
. 114
' 10
83
XX
III g
M. 75
-16
.5"
88
5 P
hen
ylh
ydra
zon
e:
XX
V e
2
3 85
M. 1
45"
m m
P m- m m
m m m o m r r m m m m m m m
N w
$
8 u
2:
m V
0 0
0 0 u m z 8 0 0
5 8
g g
0 2: U
m
705
TABLE 59. (c
ont.
)
4
0
01
N.
R
R'
R"
X
Met
hods
of
syn
thes
is
M.p
. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
15
CG
H5
CG
H5
'GH
5 C
HO
X
XV
e2
16
H
11
C,H
,
18
H
19
CG
H,
CH
, H
H
H
20 ON,,
-
H
CH
, C
H,
H
CH
3
CH
,
CH
,OC
GH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
Id
VII
I
XVn h
XX
Ve
Ia
Id
IIIb
VIL
I
IIIb
IIIb
M. 160.5-161.5"
M. 63-65"
B. 181-182"/8-9
M. 121-122.5"
M. 129"
M. 128"
M. 107-108"
B. 331-333"/145
M. 156"
M. 144"
385
812,307
388
3 84
109
941
266,301
425
307
412
414
Dim
eth
yli
mm
on
ium
d
eriv
ativ
es:
-dic
hlo
rod
iox
op
ho
s-
ph
ate:
oil
-c
hlo
rop
lati
nat
e:
M. 170" (
d.)
Oxi
me:
M. 156-158"
Sem
icar
baz
on
e:
M.>
270"
p
-Nit
roph
enyl
h y
dra
- zo
ne:
M. >
210"
A
zine
: M
. 320"
Oxi
me:
M. 129-131"
Ph
eny
lhy
dra
zon
e:
M. 142-144"
(d.)
H,O
: M. 121" (
d.)
Hyd
razo
ne:
M. 94.5"
Ben
zalh
yd
razo
ne:
M
. 127"
Ph
eny
lhy
dra
zon
e:
M. 115"
Azi
ne:
M. 114"
p -N
itro
ph
eny
lhy
d -
razo
ne:
M.
298"
22
C,H
,
23
CH
,
24
CH
,CH
,
25
C,H
,
26
C,H
,
27
C,H
,
28
C,H
,
29
H
30
C,H
,
31
CH
,
32
H
-a 33
C
,H,
34
C,H
,
4
0
CO
CH
,
CH
, C
H,
CO
CH
,
CH
, C
H,
CO
CH
,
CH
, C
H,
CO
CH
,
CH
3 C
OC
H,
CH
, H
H
H
CH
, C
H,
CH
, H
H
CH
,
H
H
Ilf
489
XX
V e
M.6
9-70
" 45
1
B. 1
33-1
37"/
11
XX
V e
M
.30
" 45
1
B.
125-
127"
/8
XX
V e
M.
59.5
-60.
5"
451
B.
184-
185"
/7
If
M
. 186
-187
" 10
3
If
M
. 20
6"
10
3
CO
CH
, V
II a
M
. 88
" 41
2
CO
CH
,Br
CO
CH
,Br
CO
CH
,Cl
812
VU
I
VIII
M.
131-
132"
94
9
XX
V e
M
. 91
.5-9
2"
451
M.
143-
144"
B. 1
80"/
8
CO
CH
,N(C
,H,)
, v1
n M
. 12
0-12
2"
812
CO
CH
=NO
H
VIII
M.
192"
(d.)
26
6
CO
CO
OH
VIII
M.
168"
(d.)
94
9
Pic
rate
: M
. 90
"
Pic
rate
: M
. 83"
Met
hyl
este
r: M
. 13
3"
2,4
-din
itro
ph
eny
l-
hydr
azon
e: M
. 22
5"
Met
hyl
este
r: M
. 15
0"
Ace
tyl
der
iv:
M.
194"
2,4
-din
itro
ph
eny
l-
hydr
azon
e: M
. 18
3"
Phe
nylh
ydra
zone
: M
. 18
2"
Pic
rate
: M
. 11
5-11
7"
'HC
1:M
. 16
0-18
0"
TA
BL
E 5
9. (
cont
.)
4
0
N.
R
R'
R"
X
Met
ho
ds
of
syn
thes
is
M.p
. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
35
C
,H,
36
CH
,
37
C
,H,
38
C
,H,
39
C
,H,
40
CH
,
41
C,H
,
42
CH
3
43
C
,H,
44
CH
,
45
C,H
,
46
C
H,
47
C
H,
CO
CO
OH
CO
CH
,CH
,
CO
CH
,CH
,N(C
H,)
,
CO
CH
,CO
OH
CO
(CH
,),C
H ,
CO
(CH
,),C
H,
CO
CH
(CH
,),
CO
CH
(CH
,),
Vll
I
XX
V e
Vll
I
VII
I
XV
II b
XX
V e
XV
II b
XX
Ve
XV
II b
XX
Ve
XV
U b
XX
Ve
XX
Ve
M. 1
66"
2
66
M. 4
3-44
" 45
1
B.
137-
139"
/10
M.
85-8
7"
425
M. 1
54-1
55"
(d.)
38
8
M.
114"
3 8
4
M.
52-5
3"
451
B.
142-
143"
/10
M.
117.
5-11
8"
384
M.
34.5
-35"
45
1
B. 1
35-1
37"/
12
M.
110.
5-11
1.5"
38
4
M.
32.5
" 4
51
B.
138-
139"
M.
99.5
-100
" 38
4
451
M.
39-4
0"
B.
175-
180"
/25
M.
36"
451
Ph
eny
lhy
dra
zon
e:
M.
207-
208"
Ag s
alt
Pic
rate
: M
. 83
-84"
'CH
,I:
M.
186-
188"
P
icra
te:
M.
166"
Pic
rate
: M
. 82
-83"
Pic
rate
: M
. 76"
Pic
rate
: M
. 11
2"
Pic
rate
: M
. 49
-500
Pic
rate
: M
. 78
.5"
48
C
,H,
49
C,H
5
50
C
H,
51
C,H
,
H
H
H
H
CH
, C
H,
H
H
CO
CH
=CH
C,H
, vm
CO
C,H
, "'
Ia
III b,
d
XV
II b
XX
Ve
52
H
H
CO
C ,H
-
53
H
CH
, C
H,
CO
C,H
,
CH
3 C
OC
,H,
55
C,H
, H
C
6H
5
CO
C,H
,
56
ON
'%
H
'ti
H,
CO
C&
2
57
C,H
, H
0%
C
OC
,H,
W
58
C
,H,
CW
, H
C
OC
,H,
mb
Vf
B. 1
81-1
90"
/10
M. 1
70-1
71.5
"
384
M. 2
50-2
50.5
"
384
M. 1
92-1
93"
45
1
M. 1
22-1
23"
81
0
M. 1
26-1
26.5
"
810
384
109
M. 1
95-1
97"
41
3
117
IIIb
M
. 155
-156
"
413
Ia
M
. 144
-145
"
82
XX
Ve
82
IIIb
M
. 163
-164
"
412
XID
M. 1
78.5
"
82
Me
82
XX
Ve
M
. 136
"
442
Pic
rate
: M
. 86"
Oxi
me:
M. 1
52-1
540
Ph
enyl
hyd
razo
ne:
M
. 13
8-14
0" (
d.)
j~ -n
itro
ph
enyl
hy-
d
razo
ne:
M.
251"
.2H
,O
M. 5
9-60
"
Ag
salt
m
> m
I m m
N
w N
N
Fd
b m
I
m
3
m 3
2 6; ii
h V .- pi
3 LD w
w w N-
m 3 >
a
* 0 N
al
j ; x
$ 8
B
d
u
V
p
m V
0 W
& 0 3
2
b w Y
.* pi
N w w
m 3
2 0 N
I m m 3
a
w
k
Lo
xu V 8
B
z?
V
V
D
m
Y u ,+ W
w m 3
& 3 3
m 3 3
I
s
al
i2 x
0
3 8 V
LD
mu
B
V
u
$ w W
t- 0 LD
3
3 w
I m m 3
r'
V
i2 x
- &7 u
1
0 0
I
m
3:
2? V
W W
m 0
0
m w m
3
N N
2
W ?
P P
E 2
I
3: 3:
$ 8 m W
N
3 m
N- e,
w CI
X $* I
x
0
I
U I
3;"
3 c-
0 m m
m' m N
In
3 m
2
d CI
h 0
m m N
In
v) N d
i
rd CI
L. 0
0 m m
d CI
e, L- m r
b (0 3
2
In c-
711
TA
BL
E 6
0.
5-A
eylp
yraz
oles
I I M
eth
ods
of
N.
R
R'
R"
X
syn
thes
is
M. p
. or
B. p
. R
efer
ence
s D
eriv
ati
ves
1 C
,H,
H
H
CH
O
g O
il
888
Oxi
me:
M. 1
77"
Sem
icar
baz
one:
M.
168"
G
uan
ylh
ydra
zon
e .H
NO
,:
M. 1
92"
2 C
H,
H
CH
, C
HO
3 C
H,
CH
, H
C
HO
4 C
H,C
H,
CH
, n
CH
O
5 C
,H,
CH
, H
C
HO
6 C
,H,
C,H
, H
C
HO
7 C
,H,
H
H
CO
CH
,
=g
M. 1
26-1
27"
88
7 S
emic
arb
azon
e: M
. 216
" G
uan
ylh
ydra
zon
e .H
NO
,: M
. 158
" (d
.)
=g
B.
80-8
3"/1
2 88
7 O
xim
e: M
. 148
"
Sem
icar
baz
one:
M. 2
06"
Gu
anyl
hyd
razo
ne:
'H
NO
,:
M. 1
59"
I1 a
M
. 116
.5-1
17"
50
5
I1 e
IJIb
Oil
88
8 O
xim
e:
jI fo
rm:
146"
\II
form
: 17
9"
Sem
icar
baz
one:
M
jI fo
rm:
166"
\II
for
m:
195"
Gu
anyl
hyd
razo
ne
-HN
O,:
M
. 196
"
487
Pro
pyl
acet
al
858
Oxi
me:
M. 1
08"
Ph
enyl
hyd
razo
ne:
M
. 136
"
8 9 10
11
12
13
14
C6
H5
H
C6
H5
C
H3
C6
H5
C
H3
C6
H5
C
H3
C6
H5
C
H3
C6
H5
H
C6
H5
H
H
CO
C6H
5
H
CO
C6H
5
H
-cO
+CH
s
H
-cJ)-c,,
cr - C
H=C
HC
[CH
(CH
,)z]
=CH
CO
-
III
b
M. 1
19-1
20"
85
8 2,
4-D
init
rop
hen
ylh
y-
184
dra
zon
e: M
. 11
9-12
0"
XX
VI
el
XXVI e
l M
. 77-
79"
988
XX
VI
el
B. 2
39-2
45"
/8
988
XX
VI
el
B. 2
32-2
37"
/7
988
XX
VI
el
B.
228-
233"
/7
988
Ia
M
. 10
3-10
4"
635
2,4-
Din
itro
ph
enyl
- h
ydra
zon
e: M
. 17
8-79
"
-CH=CBrC[CH(CH3)z]=CHCO-
I a
M. 1
68-1
69"
63
5 2,
4-D
init
rop
hen
yl-
hyd
razo
ne:
M.
229-
30"
R'
R"
R
X
XX
VI
el
M. 1
56-1
58"
98
8
B. 2
03-2
18"/
9
XX
VI
el
M.
198-
200"
98
8
TA
BL
E 6
1. P
oly
acy
lpy
razo
les.
R"' R
'yN
y ,
N.
R
R'
R"
M
etho
ds o
f R
"' sy
nth
esis
M
. p.
or
B. p
. R
efer
ence
s D
eriv
ativ
es
1 2 3 4 5 6 7 8 9 10
11
12
13
14
H
H
C6
H5
C6
H5
H
H
H
H
H
H
H
H
H
H
H
CO
C,H
,
CO
CH
,
CO
CH
,CH
,N(C
H,)
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,CH
,
CO
CH
,CH
,
CO
C(C
H,)
,
CH
O
CO
C,H
,
CO
CH
,
CO
CH
, C
H,N
(CH
,) ,
H
CH
3
C6H
5
H
H
H
H
H
H
H
CH
O
H
CH
,
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,CH
,
CO
( CH
,),
CH
,
CO
C(C
H,)
,
CO
C6H
,
CO
C(C
H,)
,
CO
C
H,
CO
C
H,
I1 a
VI
a
VII
a
VII
I
I1 c
XII
XI1
II
C
IIC
I1 c
I1 c
llc
I1 c
I1 c
M. 2
03-2
05"
M.
169"
M.
136"
M.
148-
149.
5"
M.
114"
M.
134"
M.
129.
5-1
31"
M.
108.
5-11
0.
5"
M.
144-
146"
M.
125.
5-12
6.5"
M.
113-
115"
M.
137-
139"
M.
95.
5-98
. 5"
469
Bis
-die
thy
l-
acet
a1 :
B.
137-
138"
/0~
0,
959
42 5
42 5
578
1057
10
57
578
5 78
578
5 78
518
518
578
Bis
-iod
omet
hyl-
at
e
H,O
:M.
76-9
0"
Dio
xim
e. 9
, H,O
M
. 21
7"
15
H
C
OC
H,
16
H
C
OC
,H,
17
C
OC
H,
CH
,
18
C
OC
,H,
CH
,
19
H
H
20
H
H
21
H
H
22
H
23
H
24
H
H
H
H
CH
3
H
CO
CH
,
CO
C,H
, - c
ococ
oco-
CO
C,H
, X
I1
M. 9
7"
CO
C,H
, I
IC
M
. 15
0.5-
152"
CH
3 X
XV
e
M.
50"
CH
3 X
XV
e
M.
124-
125.
5"
VIU
M. >
300"
XV
II b
-VII
I
- C
OC
(OH
)=C
(OH
)C~
-
- C
OC
Cl=
C(O
H)C
O-
-CO
CC
l, C
OC
O -
-co Q
o
OH
-co
co-
VII
I
XV
II b
VII
I
VII
I
VI
a
I11
b
XV
II b
VI
a
M.
183"
(d.)
M.
349"
M.
300"
10
57
578
94
7
11
7
407
409
40
8,4
69
409
408
408
832
386
832
Na
salt
K s
alt
An
ilin
e sa
lt
C,H
,. N
H,H
Cl
Mon
oace
tyl
deri
v:M
. 17
4"
Mon
oxim
e.
H,O
:M.
276"
M
onop
heny
l-
hy
dra
zon
e:
M.
272"
(d.)
N
-ben
zoy
l-
deri
v.:M
. 18
5"
0, O-d
iace
tyl-
der
p:
0 ,
2,N
-ii.
a<
ety
l d
eriv
.
d m a , Ln m m w Pt- *
N m a
(0 L- m
8 x 0 m N
03 0 N
b t- - k
3 m
i i i
X X X
X
m
2 V
N a N
t- N W N
M>
320"
5
8,8
87
32
C6H
5 H
C
6H
5
H
=v
g 58
33
H
CH
3 H
C
H3
=v
g M
. 346
" 5
8,7
66
,88
7
34
H
C6
H5
H
C
6H
5
=v
g 58
35
CH
3 C
H3
CH
3 C
H3
=v
g
M. 2
85-2
86"
58
36
C6H
5 'C
iH5
C6
H5
C
6H
5
=v
g
M. 3
46"
18
4
Pol
yacy
lpyr
azol
es n
ot c
omp
rise
d i
n t
he
pre
ced
ing
list
N.
Com
poun
ds
Met
hods
of
syn
thes
is
M. p
. or
B. p
. R
efer
ence
s D
eriv
ativ
es
Na
M
. 208
-209
"
966
37
CH
3-C
R
or
XX
Ve
M.
185"
83
2
I CO
C&
(D t- m
rd N (D v
d
N W v
m N (D v
d
N (D v
3
m N
LI
CI CI
Li
W
N 0 N
2
w
0
L> n x E
LI
CI c(
m 0 n v N v
v)
-r c- -r m m
i i
a'
ti
N
N al
ti
719
m a, 0
k
0 c
H
2 6
q h
In
&4 0 m v
t d t d e e m w w w w w N
U z
z +k
m
m
4
E
m W N
Ln Q) N I
m m w w
N m W W N N N N
7-l td
@
0 L n W N I
m W N
i
4
i
N In
0 0 c- c- 3
N 0, r(
4 3 td td
0" I
X 51
N m
m m 3:
w Ln W c-
720
x
x
72 I
TA
BL
E 6
5a.
4-A
min
opyr
azol
es
N.
R
R'
R"
M
eth
ods
of
X
syn
thes
is
M.p
.or
B.p
. R
efer
ence
s D
eriv
ativ
es
1H
H
H
N
H2
2H
3H
H
111
b M
. 80
-82"
XX
III
b C
XX
VII
d-1
11 b
VII
I M
. 185
"
XX
VI
b-V
III
xx
IIIb
M
. 97"
; 90"
B.
162-
164"
/15
XX
VIb
M
. 185
"; M
. 205
"
XX
VI
b-V
III
M.
176"
XX
III b
159
-2H
C1
561,
860
-2H
N0,
968
Pic
rate
:
1062
P
icro
lon
ate:
M. 1
95-1
96"
M. 2
42"
Bis
- (p
-ace
ta-
mid
oph
enyl
sul-
fo
nyl
der
iv.:
M
. 190
-192
"
326
856
449,
497,
326
-2H
C1:
M
. 195
-200
"
449,
765
326
594
0 b R c-ca 43
O N I n N 0 0 7 4
P
! x
I w 0 3
i 3
3 e O P O
m 5:
Ln
=a U
2 x u
D? m u
u,
=a U r n
ln ( D r
723
w m m n C O P -
El ?
m m P-
0 rl 0 rl
i
rl d
m 0) m d m P-
i
rl d
m co m
cn- m P-
rl d
- I d c d d d d Q
x; m; v v
m m
m 4 :
m
P
z? V
In In
% u % V
e
3 N 3 3
725
TA
BL
E 6
5a.
(con
t).
-1
N
Q,
N.
R
R'
R"
M
etho
ds o
f X
sy
nth
esis
M.p. o
r B.p.
Ref
eren
ces
Der
ivat
ives
NHCHO
NHCONH,
NHCONHC6H5
NHCSNHC,H,
-NH
CS
NH
NHCOCH,
NHCOC,H,
N=CHC,H,
XX
VIb
rn
f
XX
VI
f
XX
VI
f
XX
VI
f
XX
VI b
IMV
I b
XX
II a
1
XX
II a
1
XX
II a1
XX
II a
1
XX
In cl
M. 112-113"
M. 198"
M. 193"
M. 173"
M. 189"
M. 120"
M. 181"
B. 113"
M. 103"
M. 101"
M. 169"
M. 188-189"
710
-H,O: M.81"
710
710
710
710
710
.H,O: M. 94-95'
710
710
710
710
710
710
-HC1: M. 292"(d.)
14
C,H,
15
CH3
16
C6H5
--
NH
~H
-C
O-
CH
~ V
III
Ia
M. 239"
M. 263-264"
M. 102-104"
M. 38-40"
M. 130-131"
M. 153-154"
M. 144-145"
M. 90-91"
M. 125-126"
M. 15
5-157"
M. 160"
M. 218.5"
710
710
556
.2HC1
861,895,763 *H20.
M. 68"
365,895
763
861
918
861
763,895
365,895
910
910
TA
BL
E 6
5a.
(con
t).
Met
hod
s of
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
N
. R
R
' R
"
X
-3 N
18
C,H
, C
H3
gH
5
XX
IIIb
M
. 102
-104
"
C
XW
a1
M. 1
58-1
59"
XW
a
M. 1
56"
XW
a
M. 1
94"
XX
II a
M
. 235
"
02N
'
TA
BL
E 6
5b.
4-A
min
opyr
azol
es w
ith
Un
assi
gned
Str
uct
ure
895
365,
895
365,
895
910
910
910
-
Met
hod
s of
N
. R
R
' R
" X
sy
nth
esis
M
.p.o
r B
.p.
Ref
eren
ces
Der
ivat
ives
/CO
-CH
z
'CO
-CH
z C
6H
5
CH
3 C
6H
5
--N
I I
a
M. 1
93"
91
8
M. 1
50-1
51"
91
8
2 2 w w
P 0 m 0 1 t - w m o ~m
a m
E E I 1 * * u u + +
I
X
Xm u
$ N
z Z Z w w w
0 r.3
N * N
>
m
X
z? u
0 0
w w a m
R cd m
s
w r
729
z X X x m m 3:
730
m m W
m m W
m m W
m W
3 t-
m m W
3 L- W O
W W m L- lc
m 3
I W v) m m d 3
Y 8 E Y Y Y E E
X m X m X m 31 m m
m 3
m 3 t- i W
3
* N CT) N N N i N 0 N
73 I.
m W N
b W
z'
X
ln
m 3 Fi
n 4 w m N O W N % Z w m m
N N N m r- W
N N 3
2
Ln
t- 3
z'
W 3 3 r- W
2
0 N
W m
z'
E x E X E r n X
m m 3 N n m
w m o N N n r N
732
3 3 3 w w w w w w
m m m m t- L - c - t- w w w w
0 N I
m m t - t - m o
P 3
m 0 t-
W
N m
f'
E
X X X X
c o r n m m L- m m W
m m * 0
N W N
b m I
m m
5
I z I1
X V X V II
V V
1
- z? -
3:
Y)
5 4 1T
133
TA
BL
E 6
6.
(con
t.)
-a M
eth
ods
of
rp
N.
It'
R"
R
X
sy
nth
esis
M
.p.
or B
.p.
Ref
eren
ces
Der
iva
tiv
es
W
42
C,H
, H
-c(cH~)=cHc(cH,)=N-
IV a
-XX
II a1
M. 170-172"
261
43
C,H
, H
-C(C
H,
)=C
HC
(CO
OH
)=S
VIII
M. 225-227"
262
~(CH,)=CHC(CONHNH,)=N-
IV a-XXII a1
M. 156-158"
262
-C(CH,)=CHC(CONHNH,)=N-
VIII
M. 194-195"
262
-C(C
H,
)=C
HC
(CO
NH
NH
CO
CH
, )=N-
VIII
262
-C(C
H, )=
CHC
(CO
N-N
)=N
- VlII
M. 215"
262
II
CH
z-OC
C+CH,
Na s
alt
45
C,H
, C
6H
5
-C(C
H,)=
CH
CO
N(
XXVI b
M 69-90"
261
CH3
m m m m 6 6 $ 6
e n
x x x x 51 E E B x x x
735
TA
BL
E 6
8.
Am
inod
ipyr
azol
yls
N.
Com
pou
nd
s M
eth
ods
of
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ati
ves
1 Ix
M. 1
08"
70
3 *2
CH
,I : 2H
,O :
M.
120"
(d
.)
z z
a m
z"
2 u X" u
W fc t- t-
W W c iD c
n a P a
X X E
Ln w w w W T C .
$ t- t - t - m t-
3 3
7 D P r i e s s 5 5 X x x R r
w w i E E 6
Q D
E xx X
5
t- 0 (D t- t- t- P * (D
0 c- l- 3 3 W r- (D
N t-
D D Q Q D Q e
0 3 * v1 t- 03 N N N N
(D 00 N m N N
739
W
W
W c - i
Q I
X x
3
m
W 3
6 E;
N c 3 c t- 3
i i
Q Q
& &
3 3
0 r- W
W c 3
f.
Q
Fi x
3
a z
d V
d
8 W
-* 0 N
f'
Q
E
3
m a r
E, z 2'
r
d V
d V
v1
E * m
3
t- W LD l- W
- a
2 N
i 2
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Q Q
s X X x X
5
* 3
t- 0 2 c t-
t- W W
3 3 3
a
m z
am V xm v d
V X" V
X
01 m m m
N N N
0 (D
6 m 3
s
3 0 l- 6 W
3 m 0 m *
i s
n n
% W
8 W
0
W W m (0 z LD l- W
m 4 N
i
X z
u d t? z" u
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m m
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m
d u
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9
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P
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i
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(9 m (9 (CI a (9
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t- m i N m Ln (0 m " P a 0 M 2 " " (9 (9 Z "
743
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X" U
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01
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3 6
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3'H3
8
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H
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9
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'H3
5
H
'H3
P
H
"3 &
EH
3
2 H
H
HI
TA
BL
E 7
0.
(con
td.)
Met
hod
s of
N
. R
R
' X
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
13
C,H
, H
O
CO
C,H
, V
f
M. 170-171"
1028
XX
VI
a 1028
C
1028
14
CH
, C
H3
OC
H,
Ig
M
. 85"
101
15
CH
, C
H3
OC
2H5
Ig
M. 93
"; 98"
101,1058
16
C
H,
CH
,CH
, O
CH
3 I
g
M. 106-107"
101
17
CH
, C
H,C
H,
0C2H
5 Ig
M. 86"
101
18
CH
, C
H,C
H,C
H,
OC
ZH
.5
Ig
M
80.
5"
101
19
CH
, C
H,C
H,C
N
OC
H,C
H,C
N
**
M. 194-195"
590
20
CH
, -C
(CH
3kC
HC
0C-
XX
VI
a M. 246"
947
77 2
Ben
zoyl
der
iv. :
M. 181"
***
* F
rom
3-m
eth
yl-p
yraz
ol-5
-on
e w
ith
acr
ylon
itri
le.
Fro
m 3
-met
hyl
-4,P-cyanethylpyrazol-5-one w
ith
acr
ylon
itri
le.
Fro
m a
ceta
ceti
c ester-isonicotinoylhydrazone b
y h
eati
ng
at 150-160"
**
***
PS
9 09L '
H
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XX
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~~
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3
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3
&
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3 Z
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1
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W 03
E
cd
i
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=* V
Xrn u
m
L.l + m
W d
W 3 L- c-
5: X
W W In m m W
In In N W W W
d d
X m X m
In r(
m w rl O 3 3 3
N 3
7 4
749
TA
BL
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2.
4-H
ydro
xpyr
azol
es
N.
R
R'
R"
X
M
eth
ods
of
syn
thes
is
1H
2H
3 C
H,
4 C
H,
C6
H5
C6
H5
C6
H5
C6
H5
9 C
fiH!i
10
H
11
H
12
H
H
H
OH
CH
,CH
,CH
(CH
,),
H
H
H
H
H
H
H
OH
OH
OC
OC
fiH
5
OH
H
OC
,H5
H
OC
ON
(CH
,),
H
OC
ON
HC
6H,
H
OC
OC
6H5
CH
3 O
H
CH
,CH
, O
H
Cfi
H5
OH
111
b b, d
I11
d
M
XX
VI a
111 b
XX
VI a
XX
VI
a
XXVI a
Ih
Id
Ih
M.p
. or
B.p
.
M.
118-
118.
5"
M.
85"
Oil
M.
89"
M.
119-
120"
B.
335"
/736
Ref
eren
ces
,Der
iva
tiv
es
.HC
l: M
. 14
9-
1060
15
1"; 1
57"
129"
33
6 P
icra
te:
M.
128-
159
1060
1060
1059
456
B.
154-
155"
/0.
3 10
75
M.
168"
10
59
M.
78"
1059
M.
173.
5"
91 1
M.
179-
181"
10
81
M.
188"
91
1
.HC
l: M
. 80"
-HC
l.l/,
PtC
1,:
M.
180"
m m N
m P m 3
I LD
a I
8
s? V
31
VJ
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I 3 s 2
m m m m m ro N N N
N d
x x x
3 u
W m N m m N m ro N m m m m m m N N N
2 2 2
m
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m N 3 i
m
W 3 s
m o 4 l m m m m - 0 3
I N (D
W m
d
2 2 2 % 2 2
m
I h i
rl
m N 3 i
W 3
I N (D d
4 m 3
% 2 2
x x m 51 x X
W m N m m N
m m N W Ln
N (D m N
(0 m N
W m N
m
I I m 3
N m 4
R
I
m 3 3
3
3
N 3 i
b m i
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5 0 u X 8 8 0 0
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s;” V
97 V
a -
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m 3 3
2
d
5 @
X* V
8
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X
m m N (D m N
0 m
I m
t- m d
3
OD N 3
s 2
cd
P 5 E 3
u
8 8
X X
c m
n m
N m i
m
2 i 3
W t- d
I Ln
t- 3
T: 0 m 3
i
z? u
m
2 uq m m
m
r" V
X
4 m
0"
L n w m m co m t-
m
753
TA
BL
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2 (c
on
td.)
4-H
yd
rox
yp
yra
zole
s n
ot
com
pri
sed
in
the
pre
ced
ing
tab
le
4
cn
sr
N.
Co
mp
ou
nd
s M
eth
od
s of
sy
nth
esis
M
.p.
or
73.p
. R
efer
ence
s D
eriv
ativ
es
la
M
17
5"
17
8
VII
I M
. 98-
99"
42
3
3
HSC
v c2
M
. 71
-72"
V ~
2-V
I b
42
3
TA
BL
E 7
3.
5-A
lkox
y-
and
acyloxy-pyrazoles
N.
H
R'
R"
X
M
eth
ods
of
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ati
ves
1
CH
,CH
,OC
H,C
H,
2 C
H,C
H,C
H,
3 C
H(C
H,)
,
4 C
H,C
H=
CH
,
5 C
H,(
CH
,),C
H,
6 C
H,C
H(C
H,)
,
I C
H,(
CH
,),C
H,
8
CH
,CH
,CH
(CH
,),
9 C
6H5
10
C,H
,
11
C6H
S
12
C
,H,
13
CH
,
14
C
H,
15
C
H,
16
CH
, V
I V
I
H
H
C"3
H
H
H
H
H
OC
ON
(CH
,),
OC
ON
(CH
,),
OC
ON
(CH
.J,
OC
ON
(CH
,),
OC
ON
(CH
,),
OC
ON
(CH
, ),
OC
ON
(CH
,),
OC
ON
(CH
,),
OC
H,C
H,
OC
OO
C ,H
,
XX
VI
a
XX
VI
a
XXVI a
XX
VI a
1138
B.
110"
/0.6
11
38
B.
10
5"
/0.0
4
1138
B.
10
8"
/0.1
11
38
R. 1
10
"/0
.05
11
38
B.
11
3"
/0.1
2
11
38
,11
18
B.
115"
/0. 2
11
38
B.
11
2"
/0.2
11
38
M.
34-3
5"
1023
.H
CI.
'/2P
tC1,
:
M.
141-
143"
B.
14
8"/
0.
5 11
38
5. 1
48-1
50"
/0.
06
1075
M.
167"
31
4
5. 1
02"
/0. 6
11
38
1138
M.
196-
198"
11
26
1126
TABLE 7
3. (c
ontd
.)
-a
Met
hod
s of
N
. R
R
' R
X
sy
nth
esis
M
.p.
or B
.P.
Ref
eren
ces
Der
iva
tiv
es
11
CH
,CH
,
18
CH
,CH
,F
19
CH
,CH
,0C
H3
20
CH
,CH
,OC
,H,
21
CH
,CH
,
22
CH
,CH
,CH
,
23
CH
(CH
3)2
24
CH
,CH
=CH
,
25
CH
,(CH
,),C
H,
/CH
:, 26
-C
H \CH
,CH
:,
27
CH
,CH
(CH
,),
28
C(C
H,)
,
29
CH
,CH
=CH
CH
,
,CH
=CH
,
\CH
:, 30
-C
H
31
CH
,(C
H,)
~C
H,
32
CH
,CH
,CH
(CH
,),
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
OC
ON
(CH
,),
OC
ON
(CH
,),
OC
ON
(CH
, ),
OC
ON
(CH
, ),
OC
ON
(CH
,),
OC
ON
(CH
,),
OC
ON
(CH
,),
OC
ON
(CH
,),
OC
ON
(CH
,),
1127
et
hy
len
egly
cola
ceta
l M
. 180-1
82"
VII
I
XX
VIa
B
. 11
5-11
8"/0
.5
1O75
.111
4
B.
103"
/0. 2
11
38
1138
1117
,113
8
1138
B.
116"
/0. 3
11
38
B.
124"
/0.
3 XX
VI a
XXVI a
B
. 10
?"/0
. 15
1120
,113
8
B.1
11
"/0
.2
1138
B.
106"
/0. 3
5 11
38
B.
l08"
/0.
2 11
38
B.
124"
/0.4
11
38
B.
100"
/0. 2
2 11
38
1138
XX
VI
a B
. 10
5-10
6"/0
.18
1118
B.
118"
/0.1
8 11
38
XXVI
a
B.
131"
/0. 5
11
13,1
138
33
CH
,(C
H,)
,CH
,
34
CH
,(C
H,)
,CH
,
/CH
,CH
, 35
-C-(
CH
,),C
H,
\CH
~O
H
/CH
,-CH
, 36
-CH
)C
H,
\CH
,-CH
,
37
CH
,C,H
,
38
-,
:H
2e
%
-
39
C,H
,
H
H
OC
ON
(CH
, ),
OC
ON
(CH
,),
1138
B. 140"/0.2
1138
OC
ON
(CH
,),
H
1138
OC
ON
(CH
,),
XX
VI
a
B. 165-168"/0. 15
1075
OC
ON
(CH
,),
OC
OC
,H,
OC
H,
XX
VI
a B. 150"/0.3
lM5,
1119,1138
XX
Vl
a
M. 119"
493
B. 277-282"/125
555
.HC
l.'/,P
tCl,
H,O
: D
ec.
180-182"
476
826
400, 555, 785,
-HC
1-'/,
PtC
1,
:
979,1087
M.
180"
; 195"
476
555,1086,1089 .H,O: M. 62-63"
981,1090 a
981
981
47 6
476
732,1075,
1112
VII
I
XX
VI
a
1%
VIE
XX
VI
a
VLU
VII
I
XX
VI
a
XX
VI
a
XX
VI
a
XX
VI
a
B. 239-240"/212
B. l8O"/lO
M. 38. 5-40"
H.300-302"/752
M. 53-54"
M. 158"
M.
78"
M. 47"
M. 52"
M. 28
"
M. 50
"
40
C,H
, H
41
C,H
,
42
C,H
,
H
H
OC
H,C
H,O
H
OC
H,C
OO
H
OC
H,C
OO
CH
3
OC
H,C
OO
C,H
,
OC
OO
CH
,
OC
OO
C,H
,
OC
ON
(CH
,),
43
CsH
s
44
C,H
5
45
C,H
,
H
H
H
B. 167-172"/2-3
B. 160-16%"/0. 2
B. 151-153"/0. 3
-4
01
-4
46
C,H
, 1075
H O
CO
N(C
,H,)
, X
XV
I a
TA
BL
E 7
3. (
con
td.)
2 N
. R
R'
R"
X
m
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
'tjH
5
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
OC
ON
(CH
,CH
:CH
, ),
OC
ON
[CH
,(C
H,)
,CH
~I,
OC
ON
HC
,H5
OC
OC
H,
OC
OC
H,C
l
OC
OC
H,C
H,C
H3
OC
OC
,H,
OSO
,C,H
,
OP
S(0
C ,H
1,
OC
ZH
5
OC
OC
H,
OC
OC
,H,
XXVI a
XXVI a
XXVI f
XX
VI a
XXVI a
IX
XXVI a
XX
VI a
XXVI a
XXVI a
VIE
Ig
XXVI a
XXVI a
XXVI a
VLU
--__
~ ~~
Met
hod
s of
sy
nth
esis
M
.p. o
r B
.P.
Ref
eren
ces
Der
iva
tiv
es
-
R.
160-
162"
/0.
4
B.
170-
171"
/0.
2
M. 9
2-93
"
B.
20
0"/
10
M.
143-
145"
8. 1
72"/
8
M.
75
-76
"
M. 9
1-92
"
B.
125-
126"
/0.1
M.
195"
M
84"
B.
173-
175"
/0.
2
M.
76"
M.
192-
193"
1121
1075
1048
476
1109
679
574
47
6,7
85
476
953
139
98
0
98
0
1075
98
1
10
74
,11
25
a
1074
m m
N
0 3 E - t -
759
TABLE 73. (c
ontd
.)
Met
hods
of
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
R'
R"
X
-3 0
m
N.
R
72
JJcl
O
CO
N(C
H:,I
,
OC
ON
(CH
,),
XX
VI
a B. 163-165"/0.1
1075
H
H
XX
VI
a M
. 140-141"
1075
l4 9,,,,
1125 a
K s
alt
O
CO
C,H
, X
XV
I a
Cl -Q
SO
*Cl
M. 137-139"
1074
VII
l
OC
ON
(CH
,),
OC
ON
(CH
~;,
OC
OO
C,H
,
XX
VI
a
XX
VI
a
B. 143"/0. 1
1075,1138
B. 205-207"/0. 2
1075
75
C,H
,
76
C6H
,
CH
,CH
, H
C6
H5
H
H
77 a
XX
VI
a M
. 196-198"
1074,1125 a
M. 8
0"
1074
VII
l M
. 184-185. 5
" 1074,1125 a
E
thyl
eneg
lyco
lace
tal
1127
P
olyv
inyl
acet
al
H
H
XX
VI
a
XX
VI
a
M. 113-114"
1000
Su
lfon
e: M
. 140
M. 7
1"
313
78
79
C6
H5
O
CO
C,H
,
OC
ON
(CH
,),
'sH
5
OC
ON
(CH
,),
XX
VI
a
M. 103"
313
Su
lfon
e: M
. 156"
m n L D M
LD
0
(D N * d
t- m * I
LD m d
2
t- t- d
LD t- 3
I
n n n d n d m
31- s U 0 u
3: 3: 3: 31
3 * N . 7 m m m m LD m (0 m m t- m m
761
0 P U
8 3
0" 0
z
r" d d u u u g d z d 0 u u u
762
CH
3 O
C,H
, vi
n M. 75"
1097
CH
3 O
CO
CH
, X
XV
I a
M. 167-168"
1097
XX
VI
a-V
III
100
C,H
,
101
C,H
,
102
C,H
5
XX
VI a
M 117"
978
XX
VI a
M. 139-140"
66,964
IV b
-XX
VI a
M. 236"
432
XX
VI a
103
C,H
, X
XV
I a
M. 178"
843
.HC
1: M. 140"
843
fJ""
104
C,H
, X
XV
l a
M. 171"
843
XX
VI a
M. 138"
587
106
C,H
,
107
C,H
,
108
C,H
,
4
01 0
XX
VI a
M. 132"
947
XX
V i
-XX
VI a M. 226-221"
1070
M. 227"
161
**
* F
rom
l-p
heny
l-3,
4-di
meth
ylpy
razo
l-5-
one w
ith
m-n
itro
ben
zald
ehyd
e in p
rese
nce
of
HC
1.
Fro
m l-p
heny
l-3-
meth
ylpy
razo
l-5-
one
wit
h b
enza
ldeh
yde
and
0-n
aph
thyl
dm
ine,
or
ben
zal-
0-n
dp
hth
ylam
ine.
**
X
3 3
3 0
.L c
c
r
d V
0 - 3
164
11
5
C,H
,
116
C,H
,
117
C,H
,
118
C,H
,
1029
t tt
M
. 14
7"
1029
M.
15
8"(
d.)
tl
M
lS
l"(d
.)
1029
1029
M
. 1
51
'(d
.)
tt
119
C6H
5 '6"5
a,,,
~ t
t
M
134"
(d.)
10
29
+ * *
Fro
m 1
-hro
mo
-3,
4-d
imet
hy
lpy
razo
l-5
-on
e w
ith
NaO
H.
I*** F
rom
3,4
-dim
eth
ylp
yra
zole
wit
h N
aOB
r o
r fr
om
l-bromo-3,4-dirnethylpyrazol-5-one w
ith
NaO
H.
t F
rom
l-p
heny
l-3-
methyl-4-hromopyrazol-5-one in
eth
yl
alco
ho
l, i
n p
rese
nce
of
Na
acet
ate,
ace
tic
acid
an
d C
uS
04
; als
o i
n p
rese
nce
of
py
razo
le b
lue.
t t
F
rom
py
razo
le b
lue
and
the
corr
esp
on
din
g l-a
ryl-
3-me
thyl
-4-bron1opyrazol-5-one, in
pre
sen
ce o
f Na a
ceta
te a
nd
CuS
O,.
NR
R
' R
M
eth
od
s of
sy
nth
esis
M
.p. o
r B
.p.
Ref
cren
ces
Der
ivat
ives
12
0 -(
==
=..
12
1
H&
M.
164"
(d.
1 10
29
M. 1
62. 5
-163
. 5"
10
30
It
* F
rom
1,o
- tolyl-3-methyl-4-bromopyrazol-5-one
and
bis
-p-b
rom
oph
enyl
pyr
azol
e b
lue
in p
rese
nce
of
NaO
H a
nd C
nSO
,. * *
Fro
m 1
, o (
or p)-tolyl-3-methyl-4-bromopyrazol-5-one in a
ceti
c an
hy
dri
de,
in p
rese
nce
of
acet
ic a
cid
, Na-
acet
ate
and
CuS
O,.
m
u1
4
m
m
TABLE 74.
Po
l y h
yd
r oxy
p yra
zole
s
d
Met
hods
of
N.
R
R'
R"
R"'
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
'CiH
5 O
CO
C,H
5 H
O
CO
C,H
, X
XV
Ia
M. 111"
682
2 O
CO
C,H
, H
O
CO
C,H
, X
XV
Ia
M. 133"
43
C6
H5
O
CO
C,H
, C
H,C
H,
OC
OC
,H,
XX
VIa
M
. 120"
711
C6
H5
O
SO,C
,H,
CH
,CH
, O
SO,C
,H,
XX
VI
a
M. 189"
711
m c- N
LD m LD * *
i i
3 N
Ld
E
m t-
* T?
m
Lo-
d
767
TA
BL
E 7
6.
Hy
dro
xy
py
razo
les:
py
razo
liu
m s
alt
s
Met
ho
ds
of
N.
R
R'
R"
R"'
R""
X-
syn
thes
is
M.p
. o
r B
.p.
1
CH
, C
H,
H
OH
H
1
IV a
-c
M.
141"
c1. S
;PtC
l,
M. 2
12"
(d.)
3 C
fiHs
H
OH
n O
H
H
OH
OC
H,
H
CH
3 H
M
195"
(d.
) I
IV c
c1
Dee
. 20
3"
Cl.'
/,PtC
l, M
. 19
3" (
d.)
OH
M
. 13
2-13
5"
OH
I c1
C1.
'/2Pt
Cl,
I I I I 1.1,
IV c
M.
150-
155"
(d
.)
M.
201-
202"
M.
225"
(d
.)
M.
190-
195"
(d
.)
IV c
M
. 19
6-19
7"
(d.)
M.
198"
(d.
) IV
c
1v c
11
1.19
8"
IV c
M
. 13
0"
XX
VI
a
M.
132-
133"
Ref
eren
ces
10
60
255
255
255
255
654
5 57
557
972
W l- a t-
Ln v)
a - 2 3 I "
m w 3 Q ) i d
z ' z '
u z ,
X rn X 31 X
tT z? u
m X u
i 3 0 m 3 m
769
L- cp 3 3
i
0
2 W
I N W
a
P
6
m
B M
X
X
Ern V
3
c- f 3
m m I m m
2
P
E
m G M
m
X
n Xw V
m
t- f 3
& W
I m m
2
P
6
m B M
6
X
t7 cp
In 0 3 3
h
a v
LD m s:
a
6
m m V
X
LD
E 0 ?I
7-70
Ln
0 3 3
P
Ln
0 3 3
W
5 2
P
ti x
0" 0" I I
m a
N i ,+ 3
0 W Ln
id I
3 3
711
4
4
Lv
TA
BL
E 7
8.
N-u
nsu
bst
itu
ted
3-
or
5-th
iop
yraz
o1.e
~
Ru
x
R'
/I
Met
hod
s of
Der
iva
tiv
es
N.
R
R'
x sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
1H
H
SC
HZ
CG
H,
I11
c 91
3 P
icra
te:
M. 11
0-11
1"
2H
C
H3
SCH
, III
c
3H
C
H,
SCH
,CH
3 I11
c
4H
C
H,
SCH
,CH
,CO
OH
I11
c:
913
Pic
rate
913
Pic
rate
913
Pic
rate
M. 1
64-1
65"
M. 1
32-1
33"
M.
134-
135"
Pic
rate
:M.
145-
145.
5"
5
H
CH
3 SC
H,C
GH
, I11
c 91
3
6 C
,H,
C,H
, SC
H,
Xe
M
. 16
0"
162
Ace
tyld
eriv
: M
171"
SO,C
H,
g M
. 25
0"
162
TA
BL
E 7
9.
3-T
hio
pyr
azol
es
N.
-. 1 2 3 4 5 6
R
R'
R
X
Met
hod
s of
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
C6H
5 C
H,C
H,
CH
,
SCH
,
SO,C
H,
SCH
,
SO,C
H,
SCH
,
SO,C
H,
SCH
,
SO,C
H,
SCH
,
SCH
,
B. 327"
B. 175"/10
M. 105"
M. 62"
M. 121"
B. 135"/32
M. 122"
B. 151"/31
M. 85"
M. 40"
B. 205-208"/20
B. 160-165"/12
~ ~
~ ~~
~~~
655
.HC
1: M. 132"
655
.HC
1.l/,
PtC
1,.H
,O
: M
. 130
" (d
.)
655
913
720
720
720
656
656
656
656
684
684
p:
i 3 N
7 7 4
R m
I d m 3
3 * 3
I 0 -
3
s z
m 0 0 4 9 m
m m m" 0 0- 0 F- m m 6 fs m ffi N O 3 3 m m 3 - N 3 4 % 2 0 N m d
9 V
V d g zw
d u d d U O
d U
r: > *
m
m- m m
rr W
r r r r w W ' W w
w w m m m cc w w w
0 ( 0 3 t - - 4
2 2 r w 0 o w m i
I I w m 2- o w m + m
3
rr 3
n o j c j
m* 0
m
m
2 V
m m m e r r cy w w w
m
m
Z W V
m
776
C6
H5
C
H3
H
SCH
(CH
,),
M
B. 3
09-3
10"
64
9
B.
176"
/16
M. 8
3"
649
M.
56-5
7"
649
B. 1
84-1
88"
/11
B.
313-
314"
64
9
B. 1
68-1
75"
/9
B.
246"
/20
649
M. 9
2"
649
M. 9
3"
70
0,7
01
701
Oil
70
1
Oil
70
1
SO,C
H(C
H,)
,
SCH
,CH
=CH
,
g
XX
Vl
d
' C
6H
5
H
C6
H5
H
M
C6
H5
H
SC
H,C
6H,
S0,
CH
,C6H
,
SCO
C6H
, 10
C
6H5
H
11
C6H
5
12
C6H
5
H
H
"O2
6 H
S
-S-S
yJC
H3
I C,H5
SCH
,
SO,C
H,
SCH
,
SO,C
H,
SCH
,
M
M.
61"
M.
160"
67 1
14 AN''
M. 84"
67
0
670
M. 1
35-1
36"
64
9
M. 1
39"
672
M. 15
4"
67 2
M. 1
32"
67 2
.HC
1: M
. 18
5"
.HC
1: M
. 221
"
S0,
CH
3
SCH
, H
W W 9 9 9 % 9 s 3 L o w w w w (D t-
N 3 3 3 3 L D W t- N N N N w w w t - P t - t - w w
P 3 m m 3
3 E X I N I 2 1 3 N N N 0
778
I I
l l 'e:
e:
i
;6" x
s m
D I c u m m m
N
A N
x x :I
TABLE 8
3.
Th
iop
yraz
oles
not
co
mp
rise
d in
th
e p
rece
din
g ta
ble
s
-
4
0
Met
hod
s of
m
N.
Com
pou
nd
s sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
1 2 3 4
I I
C6
H5
C
GH
S
* **
Ix
IV c
IV c
M. 12
4"
M. 14
9"
M. 19
8"
665
665
703
703
M 1
98
M. 23
4"
665
703
XX
Vl a
M. 1
34"
70
3
XX
VI
a B
. 72
-76
"/2
10
78
* F
rom
1 -ph
enyl
-3-methyl-4-bromo-5-benzoylthiopyrazole b
y h
eati
ng
at 1
50"w
ith
HC
1.
** F
rom
bis
-[ t-pheny1-3-methylpyrazolyl-(5)~-disulfide by
vac
uu
m d
isti
llat
ion
.
181
2 m e r x x e m T m m m
782
1 8 3
W W W
cu 3 >
a
3
W 3
E
mm % M
m
mm u
m
3 cu
w w w m W c o co co w w w w
m 3
g s a a
m m
m
xQ mm u u
784
m
v1
* d
.d $
.-(
N
I n" . I
m d
N
b !a a c r(
rn
W m W ;I a E
m m m m w w
0 CO 3
s
cd
0 5 e N
U
mi u
m
Em v m
mm u
m: u
,-I
(D W -F W (D
m
cu m 4
m 0 N
cd cd
E E U
mm ON
v m cn
m
mm u mm u
Em u mm u
e- co
785
W W
W W m m
d
4 Q I
m m
z? 0
z? u
a
u
0 3
d
0 r 0 m m
/
3
786
‘ I I
4 m
4 h
z
p:
rd n
X
s N 3 I n N 3
Zi
rd w
X z? V
% W
A a, m
A
0 t- m 0 L- m
v 3 3
m v N
f A
787
TA
BL
E 8
8.
Pyr
azol
e T
hio
, Su
lfon
ic, a
nd
Ph
osp
hon
ic A
cid
s an
d t
hei
r F
un
ctio
nal
Der
ivat
ives
Met
hod
s of
N
. R
R
' R
" R
'"
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
TA
BL
E 8
8.
(con
td.)
Met
hod
s of
-4
m
OD
N.
R
R'
R"
R"'
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
4 C
SSH
C
H,
H
'GH
5 24
0
5H
6H
7 C
6H5
H
H
H
CH
,
CH
, H
9H
10
H
11
H
H
SO3 H
CH
, SO
,H
CH
, SO
,H
S0,
CI
SO,H
V
I a-
VII
I M
. 25
7"
889
Pyr
idin
e sa
lt:
SO,N
(C,H
,),
VI
a M
11
2-11
3"
M.
169-
170"
889
M.
275"
88
9
SO,N
(C,H
, ),
VI
a M. 1
27"
889
SO,H
X
XI
h M
. 235
" 7
01
N
a sa
lt
Ba
sa
lt
SO,H
V
I a-
VII
I
S0,
CI
VII
I M
. 10
1"
70
1
SO,N
H,
VII
I M
. 243
" 7
01
SO,N
HC
,H,
VII
I M
. 127
" 7
01
SO,H
X
XI
h
M. 2
46"
685
Ba
sa
lt
S0
,Cl
VII
I M
. 77"
68
5
SO,N
H,
M.
227"
68
5
so,N
HcG
FII
j M
. 11
8"
685
H
XM
e
M. 3
45"
(d.)
88
9
H
XM
e
M. 2
57-2
58"
548
Ba
sa
lt
CH
3 X
M e
73
9 .1,
5.H
,O:
M. 2
87-2
88"
Ba
sa
lt
VII
I M
. 98-
100
" 73
9
XM
e
449
N l?
I
L- 3
2
m d d Ln
d d a a a m o m N N N N m 51 1 3 3 3 + *
< V
z? V
N 3
m d d
n 1
2 L- 3
I m L- 3
a
a,
6
Xm 0
X
2 V
3:
a 1
m
rn c M
.- M
N h
F4x d
c m Y
3
3 m
9 .A 0
1 0
rn
0 N
t-
Lo W N
d :
c
!
c
LD
xu V
X
r" u
W m W
co t- N
2
* n +
0" rn
X- U
X
m X V
N m *
W W m
a v
t- N N
2
3 u
>
$
X
6r
z? V
Ern u
3
7 90
m 0 t- N 3 3 m m m t- @a N v w * w t- t- w w w
0 t- W w n n r o i
w w ( D w (0 w m a a w e m t-
3
N m
9
x 3 1
c o t - 00 m o d N 3 - i
N n v u5
791
TA
BL
E 8
9.
(con
td.)
-1
a
h)
Met
hod
s of
X-
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ati
ves
N.
R
R'
R"
R
"'
13
C,H
, C
H3
CH
3 H
S
eO,
XX
I h
64
6 .H
,O:
Dec
170
"
c) D
ipyr
azol
yls
N.
Com
pou
nd
s M
eth
ods
of
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ati
ves
XX
l h
703
a" 3 E
: a,
0 a 0 u 0
.d
h 0 N cd k
+
a" 0
W IJ
Q,
a s
cd v (D co
cd (D W m
In cv W
e
5! ti
7 93
0 * (D m * W
F m N
2
W v
Q B
0 3 Lo N
W W
B E
X X
N m * LD
794
d t- o v) 0 t-
5 B 2 s
N
& 0 N N
P P
B B
W o t-
U x R
h W o W
0 t- W o t-
U U U
X B fi R
X
m
??
W t- m
795
r * 0
3
3 0
g
d
5
m
XW V
I
X
X
n
3
r N
I (0 N
3
9
N Lo i
i
d .- I I
X
X
n
Ew 3
z
X
N
796
P N n
id w
X
n
N d P N * t- f i
N
t- v) N
v) In N
N v) N
3 In N
I I - N m
i i i
P P
d 3 1 ) X ?rj 8
P i 0
d W m m
P
* m
2" 0
2" 0
Ern U
Xrn u
Xrn $ U tT U $
X m X X
* In (0 t-
$ U
X" U
X
W
Ln N N
P
d m
3 * N 3 LD N
s i
Ln
% U
d U
X" U U =-% i
i z m z
Y' ur U
T r n E El
Fr 0
m 3 *
797
G m
798
0 '
5 N I
N LD N m i%
X m m
g U m" g
x m N N N r( N
799
800
QO z
I1 1
Ln W 0
i v N
id M
X- U
d U
x? U
Xi U
m
9 U
Lo W 0
f Xrn U @ - $
0 I,
41
C
6H,
CH
3 C
6H
5
42
C6H
, C
H3
C6
H5
43
C6
HS
C
H3
'SH5
44
C,H
, C
H3
C6
H3
45
C6H
5
46
C,H
,
47
C6H
, C
6H
S
C6
H5
d')
4-a
zop
yraz
oles
wit
h u
nas
sign
ed s
tru
ctu
re
N=N
CsH
5
V b
3
la
XW
I b
l
XX
VII
a
V b
3
la
M
158-
159"
78
2
M. 13
1"
365
M. 24
7"
895
M. 2
11"
910
M. 16
9-17
0"
782
M. 22
7-22
9"
365
la
M. 15
6-15
7"
164
322
1
Met
hods
of
N.
R
R'
R
X
syn
thes
is
M.p
. o
r B
.p.
ReI
eren
ces
Der
ivat
ives
m 0
c
la
M
. 166
-167
" 22
5 'SH5
CH
3 C,HS
.
a
i l
v P-" 1:
i I - N
802
TA
BL
E 9
2.
Hy
dra
zin
op
yra
zole
s
N.
R
R'
R
X M
eth
od
s of
sy
nth
esis
M
.p. o
r B
. p.
Ref
eren
ces
Der
ivat
ives
1H
2H
3H
CH
, C
H,
CH
, C
H,
CH
, C
H,
C6
HS
H
C
H(O
H)C
H,O
H
H
-CH
(O
H X
HO
H
I 5
C6H
S
HO
CH
,
m
CH
(OH
)CH
,OH
0 0
/C*C
H:,
-NH
N=C
X
M d
\C
OO
C,H
,
-NH
N=
C(C
GC
H,)
, X
IX d
,CS
CH
3
--NH
N=C
, X
M d
C
%C
,H,
NH
NH
C,H
, I
j
NH
NH
C,H
, I
j
NH
NH
C,H
5
M. 157"
7 3
9
M. 184" (
d.)
7 39
M.
169-
170"
7
39
Fro
m L
-ara
-
bin
ose
:M
. 18
1-18
2"
334
Fro
m D
-xy
lose
:
M.
179-
180"
Fro
m D
-glu
cose
33
4 A
cety
l de
riv.
: M. 17
0"
Ben
zoy
l de
riv.
: M
. 16
0"
Fro
m D
-gal
acto
se
Ace
ton
e de
riv.
: M
. 16
8"
Ace
tyl
deri
v.:
M.
177"
Fro
m l
acto
se
334
Ace
tyl
der
iv:
M.
195-
96"
Fro
m c
ello
bio
se :
M.
245"
(d
.)
Fro
m L
-ara
bin
ose
:
334
M.
177-
178"
Fro
m D
-xy
lose
: M
. 18
8-18
9"
Ace
tyl
der
iv:
M.
180-
198"
P --2 3
c n n P m 0 e m m W
LD LD s c
h
4 :: i s
(0 Y) 3
N
U U
H H
r"
d rn 31 U
d d u d U
Y) Y)
U 4 3 d m 3 N 3 3 3
M
805
TA
BL
E 93
(con
td.)
N.
R
R'
R"
X
Met
hod
s of
sy
nth
esis
M
.p.o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
3 C
,H,
CH
, C
H,C
H,
-N=N
NH
X
IXd
M
. 10
1" (
d.)
736
H5C
z1N
J
CH
3
M.
86"
736
TA
BL
E 9
4.
Met
al P
yra
zole
s
a)
R" 'nR'
y'' I R
N.
R
R'
R"
X
Met
hods
of
syn
thes
is
M.p
. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
C6
H5
H
C6
H5
H
C6
H5
H
CH
3 C
H3
5 C
H3
CH
3
6 C
H3
CH
3
7 C
H,C
H,
CH
,
8 C
H,C
H,
CH
3
9 C
H,C
H,
CH
,
0 4
10
C6H
5 C
H,
H
H
H
CH
3
CH
3
HgC
l
Hg
Br
HgO
CO
CH
,
HgC
1
Hg
Br
-Hg)I
"M.cH
3 I
H3C
hH
3
Hg
oH
HgC
l
Hg
Br
HgC
l
M. 2
26"
380
448
M.
212-
213"
44
8
M.
191"
3
80
448
HgC
1, : M
. 238
"
448
-Hg
Br2
: M.
144"
-l/,H
gBr,
: M
. 20
4"
M. 22
5"
448
M. 22
3"
44 8
448
'HgC
1,:
M.
229-
230"
448
.HgB
r, :
M.
140"
448
.HgC
l, : M
. 17
0"
E- E- L- E- m m
0 Ln
a; 0 N Ln
I e + 0 E- N N
0
s T:
M M
ki i x
3 N m
808
& W 3
n m e W m m
& N 3
I I L- N 3
3 W 3
OD In 3
809
I
3
3 P-
b w
4 0 0 0
I 3 In 3
N v) H
& m
I I I m O P - W o w w
t-
I W
(D (D
I
c' m 3
W m I I
m m m b
5 2 2 4 3
3 3 3 - 3 3 d 4
d d d
W
d d d
9 C
H,
I
VII
I
P
NHNO,
-c\
M.
123"
93
3
M.
158-
159"
94
3
M.
167"
9
34
XM a
94
3
XIXa
M. 1
53-1
55"
93
8
10
C
H,
c1
'ljH
5
CO
OC
H,
XM
a
M. 9
7"
54
.HN
03
-Pic
rate
:
M. 2
24"
I H
R'
X
Met
hod
s sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
1 B
r n
CO
OH
VIII
M.
240"
(d.)
7
68
XV
II a
7
68
XX
V b
506
TABLE 95
(co
ntd
)
m
c.
N
Met
hod
s of
R
' X
sy
nth
esis
M
.p.
or
B.p
. R
efer
ence
s D
eriv
ati
ves
N
. R
21
3 c1
4 B
r
51
6 C
1
I B
r
8 C
H,
9 C
6H5
CO
NH
,
H
CO
OH
CH
3 C
OO
H
Br
Br
C-,H
5
CO
OH
C-,H
5 C
ON
H,
CO
NH
NH
,
CO
N,
CO
OH
CO
OH
CO
OH
CO
OH
CO
OH
XIX
a
XV
II a
-III
b
V d
2
XM
a
V d2
Vf
XM a
VII
I
VII
I
XIX
a
VJII
VlI
I
XVII a
VI
a-X
M a
XM a
XIX
a
v fl
M.
220
M. - 10
" (d
.)
M. 259"
M. 103-104"
M. 256-251"
M. 105-108"
M.
264"
(d
.)
M.
270"
M. 230-231"
Dec
. 125"
M. 237"
M. 258-261"
M. 256-257"
M. 260-261"
M. 223-223.5"
168
139
Ag s
alt
718
60
60
178
60
60,168,887
60, I
18
.HB
r: M
. 188"
168
168
118
118
139
54
59
59
508
389
Ben
zoyl
der
iv :
M. 269-70"
Ag
salt
* * * m c - c - c - w - - w w w m c - t -
8 g g
X G $
TA
BL
E 9
5 (c
ontd
.)
m
A
N.
R
CL
R'
R"
X
Met
hod
s of
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
CO
OC
H,
vm
M. 8
0-81
.5"
72
C6
H5
/ C
H,
Br
-CH
1
CO
OH
'C
H,
XIX
a M
. 184
" 88
8
VIII
M. 7
8"
888
XM a
M
. 176
-177
"
241
CO
OH
X
Ma
19
9 1
0
C,H
, B
r C
6H5
11
C,H
, c
1
c1
C
OO
H
XM a
M
214"
67
4
12
C6H
, B
r c
1
CO
OH
X
Ea
M
. 222
" 67
4
Met
hod
s of
N
. R
R
' R
" X
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
'$5
c1
C
H3
CO
OH
CO
Cl
XVII a
M
. 216
" 88
5
VII
I M
. 57"
88
5
CO
OC
,H,
VII
I M
. 93-
94"
88
5
C6
H5
c
1
CO
OH
Co
cl
V b2
M. 2
23-2
24"
32
, 34
9 A
nh
ydri
de : M
. 178
"
XV
II a
M
. 228
-229
"
71
9,8
85
V b
2-V
III
M. 8
5"; 8
7"
349
CH
, c
1
6OO
H
4H
B
r B
r
CO
OC
H,
CO
OC
,H,
CO
NH
,
CO
NH
C6H
,
-CON
HNH c
1
I
CO
OH
CO
OH
VII
I
VII
I
VII
I
VII
I
VII
I
VJl
I
71
9,8
85
M. 7
4"
349
M. 6
8"; 7
4"
349,
885
M.
183"
; 195
" 7
19
,88
5
M.
156"
88
5
M. 2
48"
885
667
VII
I, X
VII
a
M. 2
26"
(d.)
V c
6
M. 2
84"
(d.)
50
6
Met
hod
s of
N
. R
R
' R
" X
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
C6
H5
H
c1
C
OO
H
CO
OC
H,
2 C
H,
H
Br
CO
OH
3 C
H,
UI
4 C
H3
cJ43
c1
C
OO
H
CH
3 B
r C
OO
H
XV
II a
-XIX
a
M. 1
85"
858
VII
I M
. 62
" 85
8
XM
a
M. 2
32-2
34"
(d
.)
506
XX
V b
XX
IV a
M
. 225
" 50
4
XIX
a
M. 2
32"
71
Ag
salt
: Dee
. 120
"
TA
BL
E 9
5 (c
ontd
.)
m
c.
m
N.
R
R'
R"
X
Met
hod
s of
sy
nth
esis
M
.p.o
r B
.p.
Ref
eren
ces
Der
ivat
ives
5 C
H,
C6
H5
6 C
H,C
H,
CH
,
7 C
H,C
H,
C6
H5
8 C
H,C
6H5
CH
3
9 C
6H5
CH
3
10
O
Br
C
H,
f) o
ther
s
l3r
CO
OH
Br
CO
OH
Br
CO
OH
Br
CO
OH
Br
CO
OH
Br
CO
OH
XM
a
M.
208"
7
8
XM
a
M.
159"
71
M.
154-
55
" 78
M.
176-
77
" 7
2
.HB
r: M
. 194
"
XM
a
M.
179-
180"
38
6
VII
I M
. 237
"
386
N.
R
R'
R"
R"
~~
~~~
Met
hod
s of
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
1H
C6
H5
CO
OH
B
r
CO
OH
B
r
CO
OH
C
OO
H
CO
OH
X
VII
a
M. 2
74"
768
XIX
a
768
CC
mH
XVII a
M
. 244
" (
d.)
11
2
XIX
a
112
Br
VII
I-X
M
a M
. 197
-199
" (
d.)
119
NH
,+
salt
: D
ec.
190-
192"
Pb
-sa
lt
W m m 5: m
d *
m
X
4 N
z? V
sc)
817
0 m m
m w m - w w o w m w m N W N W W ~ W P W P m c - c o P P m P P t - t -
0" 2
818
CO
OC
H,
XX
Ia
M. 1
93"
421
4 NO,
ON
02
C
OO
H
VII
I-X
IX
b
M. 1
84-1
85"
82
3
XV
II a
82
3
3 NO,
C6
HS
Ia
42 1
.H
,O:
M. 1
04"
(d.)
5
NO
C6
H5
C
OO
CH
,
c) n
"n
n'
X N'
~~~
~~~~
Met
hod
s of
N
. R
R
' R
" X
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
1 C
6HS
NO
, H
C
OO
H
XVII a
M. 165"
422
2 C
H,
CH
, N
O,
CO
OC
,Hs
IVa
-Vm
M
. 72"
76
6
3 0%
C
H3
NO
, C
N
V c
6
M. 1
69"
886
d)
Nit
rop
yraz
olec
arb
oxyl
ic
Aci
ds
Not
Com
pri
sed
in t
he
Pre
ced
ing
Ta
ble
s
N.
Com
pou
nd
s M
eth
ods
of
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
XVII a
M
. 205
" (d
.)
497
K s
alt
: M.
286-
288"
m
1
c.
W
HO
OC
02N
gcooH
TABLE 9
7.
Acy
lpyr
azol
ecar
box
ylic
A
cid
s an
d t
hei
r F
un
ctio
nal
Der
ivat
ives
.
N.
R
R'
X
Met
hod
s of
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
1H
C
HO
C
OO
H
VIII
M. 2
45"
495
CO
OC
H,
II
a
M.
135"
49
5
2H
3 C
H,
4 C
,H,
6 C
H,
Cm
H,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,CO
CH
,
CO
OH
V
IJI
M.
257-
269"
78
6
XV
II b
81
2
CO
OC
H,
IIC
M
. 11
2-11
2.5"
78
6
CO
OH
I1
d
VIII
CO
OC
H,
IId
CO
OC
,H,
I1 d
CO
OH
CO
OC
,H,
CO
OH
CO
OC
,H,
VII
I
I1 d
IId
VII
I
M.
157-
158"
M. 1
21-1
24"
B. Z
02°/
26
1057
539,
540
540
389,
540
,105
7
M.
208"
10
57
M. 2
14.5
-215
" 38
9
M.
113"
38
9,10
57
M.
222.
5-22
3"
389
M.
121-
123"
20
0
Der
ivat
ives
Oxi
me:
M. 2
41-2
42"
Sem
icar
baz
one :
M. 2
10-2
12"
.H,O
: M
. 23
3-23
5"
Oxi
me : M
. 16
5"
Ph
enyl
hyd
razo
ne :
M. 1
97-1
98"
Sem
icar
baz
one
.4H
20
: M
. 220
-221
"
7 C
H,
8 C
H,
CO
CH
=CH
C,H
,
Cw
6H
5
CO
OH
CO
OH
VIII
VIII
M. 231.5-233"
200
M. 233"
389,1057
M. 239-240"
389
M. 121-121. 5"
389,1057
M. 211-211. 5"
389
M. 128-128. 5"
389
CO
OC
,H,
CO
OH
CO
OC
,H,
IId
IId
I1 d
C6
H5
C
w6
H5
-c
o~
oc
",
-
10
CH
, C
OO
H
CO
OC
,H,
VIII
I1 d
M. 220.5-221"
389
M. 216-217" (d.)
584
M 179-180" (d.)
469
11
C6H
5
12
CH
O
CO
OH
II
d
CH
O
CO
OC
,H5
IIa
Bis-diethylacetal
13
CO
OH
CO
OC
,H5
VIII
VI a
M. 281"
316
M. 186. 5"
37 6
-co'
'c
o-
14
CO
OC
,H,
M. 245-241"
(d.)
131
VI a
,OH
,O
H
-coc
= cc
o-
15
-
CO
OC
,H,
VIII
4 69
-CH
,CO
OH
: M. 217-219"
TA
BL
E 9
7 (c
ontd
.)
N.
R
R'
R"
X
1 C
OC
H,
H
CH
3 C
OO
H
CO
OC
H,
CO
OC
,H,
2 C
OC
H,
CH
3 H
C
OO
H
CO
OC
H:,
3 C
OC
H,
CH
3 C
H3
CO
OH
CO
OC
H,
4 C
OC
H,
--C
H2C
H2C
HzC
Hz-
5 C
OC
H,C
l H
6 C
OC
,H,
H
CO
OC
H,
CO
OC
,H,
CO
OC
,H,
CO
OH
CO
OH
Met
hod
s of
sy
nth
esis
M
.p. o
r B
.p.
Ia
M
. 17
3-17
4"
XX
V e
M. 6
7-68
"
B.
141-
143"
/14
XX
V e
M
. 19
8-19
9"
M. 9
8-99
"
B.
134"
/12
XX
V e
M
. 197
-199
"
M. 8
2-8
3.5
"
B. 1
55-1
56"
/14
M. 7
8"; B
. 18
2"/1
8
M. 9
4-95
"
B. 1
82"
/10
XX
V e
M
12
7.5
-12
9.5
"
Ia
M
. 18
0"
Ia
M
. 222
-224
"
Ref
eren
ces
Der
iva
tiv
es
60
58,
60
58,
60
58, 6
0
97
97
58
60
60
X
X" V
'i co
9 2 0 ln
Y V Xi?
w 5 3
N r3 * L-
W r3
3 .3 Y
al c A n
m
823
b w 3
* * 3 3
2 s
d
F F
8 8 8 8
u 8
:$
h
a v
" 0 % $ L m r ( D N 2 N 1 3 3 3
1 N C - m 3 3 2 W I il 3
- a v
N C ? N N
824
3 3
m c o w m m m m m m m m m w m m m m m a m m w m c o m m m m n n n m c o m m m
c - c - w w 1 3 c o n N N
* * * * 3 3 3 3 m 1 *
b m I
4 m
3
m
h
a v
& & h P - 3 3. 3 3 N
0 0 0 D N N w m 3 1 0 w N 3 N
0 0
3
I n 4 1 m m N 3 "oh & & oc- m r N 3 N 3
Ln (0 3
r' 2 2 A S 2 $ A r ' A r' r' r ' r ' A
u3
V u v u
m N m 3 m
0 n c - c o N N N
Ln W N N e N
825
I I
p 2" V
: 8 2 e: v v
$ i 8
I I
2 3 N m
4. m k
2
x
b:
m m r - m m
m m
I zm ZT v v
826
4 5 6 7 8 9 10
11
12
13
CH
,
CH
,
CH
3
C6
H5
CO
CH
,
CO
OH
CO
CH
,
H
CO
C,H
,
CO
C6H
,
CO
CH
,CO
CH
,
--C
OC
H=C
H
I C6H
5
I -C
OC
H,C
O
C6
H5
CO
C,H
5
CO
CH
,
CO
C,H
,
CO
OH
CO
OC
,H,
CO
OC
H,
CO
OH
'OO
CZ
H5
CO
OH
CO
OC
,H,
C6H
S
H
CQ
CH
, C
6H5
CO
OH
CO
OH
CO
OC
H,
CO
OC
,H5
CO
OH
CO
OC
,H,
CO
OC
H,
CO
OH
CO
OH
CO
OC
H,
CO
OC
H,
CO
OH
CO
OC
H,
CO
OH
CO
OC
H,
VIE
VIII
VIII
VIII
M. 179-180"
200
M. 267-268"
200
M. 177-178"
2 00
M. 109"
200
VII
I M.
IV a
81 -182"
VII
a
M. 01"
XV
II a
M. 220" (
d.)
VIII
M. 176" (
d.)
VII a
M. 158-159"
M. 84.5-85"
VII
I M. 199-200"
VII
a
M. 129-130"
VIII
M. 185-190"
(d.)
VII a
M. 136-138"
389
389
425
1057
413
p-N
itro
ph
enyl
- h
ydra
zon
e :
M. 258-261"
61
810
810
413
413
TA
BL
E 9
7 (c
ontd
.)
OD
N
m
R'
R
N.
R
R'
R"
X
Met
hod
s of
syn
thes
is
Mp
. or
B.p
. R
efer
ence
s D
eriv
ati
ves
1 C
OC
H,
C6H
5 H
2 C
OC
H,
H
'CjH
5
3 C
OC
H,
-CH
2CH
2CH
2-
4 -c
:b
-
H
H
5 C
OC
H,
CO
OH
H
6 C
H,
CH
3 C
O-C
H,
7 C
H,C
H,
CH
3 C
OC
H,
CO
OH
CO
OC
H,,
co
oc
2H
5
CO
OC
,H,
CO
OH
CO
OH
CO
OH
CO
OC
H,
CO
OC
,H,
CO
OH
CO
OC
,H,
XX
V e
XX
V e
XX
V e
XX
V e
VII
I
VII
I
IV a
VII
I
IV a
M.
162.
5-16
4.
5"
M.
12
9.5
-13
0.5
"
M.
109-
110"
M. 6
7. 5
"
M.
195-
196"
M.
169"
M.
189-
191"
M. 1
10-I
IP
M. 8
5-86
"
M. 1
67-1
68"
M. 5
7- 5
8"
58
61
67
86
58
409
54
0,3
79
379
540
540
540
10
.d ?2
B
C
c .3
m a,
a, w
d
4 m 8
4
N m m W d m m m m
0 a t- 0 N ln
3 m m m
3
3
3 3 n
fe m 3
*a
0
!+ 0
il 0
X Y
3 N m * v)
829
f) A
cylp
yraz
olec
arb
oxyl
ic a
cid
s n
ot c
omp
rise
d in
th
e p
rece
din
g ta
ble
s
N.
Com
pou
nd
s M
eth
ods
of sy
nth
esis
TA
BL
E 9
8.
Am
ino
py
razo
leca
rbo
xy
lic
Aci
ds
and
thei
r F
un
ctio
nal
Der
ivat
ives
N.'
R
R'
R"
R"'
Met
ho
ds
of sy
nth
esis
CO
NH
,
CO
NH
,
H
H
H
H
CH
3
NH
,
FN
C6H
, o
r C
H,
-N
=n
NO
*
CH
3 o
r C
,H,
w
CO
OH
NH,
H
CO
ON
H,
CO
OH
N
H,
XX
II a
XX
II a
VII
I-II
I b
XW
I b
XX
III
b
XX
III
b
XX
III
b
XW
I b
* XX
VI
b-V
IU
**
-
* B
y d
rop
pin
g a
mix
ture
of
dia
zoac
etic
est
er a
nd
cy
anac
etic
est
er i
n a
so
luti
on
of
NaO
C2H
,. * *
Frn
m e
thy
l cy
clo
pg
nta
no
neo
xal
ate
wit
h h
yd
razi
ne
hy
dra
te.
Ref
eren
ces
Der
ivat
ives
M
.p.
or
B.p
.
M.
227"
91
0
M. 23
5"
910
M.
212.
5"
(d.)
15
9 C
u sa
lt
M.
205"
(d
.)
879
M.
181-
182"
87
9
M.
185-
190"
77
8,88
0 .H
Cl:
M.
220"
M.
208"
(d.
) 77
8
M.
209-
211"
77
8
M.
168-
169"
42
1
M.
144"
15
9
M.
227-
228"
92
4
M.
165"
86
TA
BL
E 9
9. Hydroxypyrazolecarboxylic
Aci
ds
and
th
eir
Fu
nct
ion
al D
eriv
ativ
es
I X
N.
R
1 C
H,
2 C
H,
3n
4 C
H,
5 O
CO
N(C
H,)
,
R'
OC
H3
OC
OC
H,
OC
OC
H,
OH
H
b'
I
N.
R
R'
Met
hod
s of
sy
nth
esis
H
CO
NH
, l
a
H
CO
NH
, I
a
XV
UI
c
CH
, C
ON
H,
Ia
CH
,CH
, C
ON
H,
Id
CH
, C
ON
(CH
,),
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
M.
173"
M 1
82"
M. 1
26"
M. 1
87-1
89"
756
7 56
842
84
2,7
56
1081
1040
X
Met
hod
s of
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
1 O
H
H
m
W
2 O
CO
C,H
, n
CO
OH
CO
OH
If
M
. 208
-210
"
1060
111
b-V
III
M. 2
04-2
05"
15
9
If-XXVI
a M. 21
0-21
2" (
d.)
10
60
XX
VI
a 10
60
r m N
t a H
X
N
0 In N
I 0 N N
c
M
.- c.'
m c R n 9 s V
R .+ 3
tj
g u I m
3
R a R
? 3 R
2 B E e 3
F t
L- m 3
I (0 m 3
%
3 : ' X
3 v) N
r v) N
r v) N 0 5: s z
Ln N N N 0 In N
N
v)
* 0 4
x x x x x X 5:
L% N
m
m 3
N .3
3 LD t- m m 2 *
833
c- m N
R v) 3
I L c 3
E'
a c(
v)
9 8 u
X
8
4 U
rn v) N
v) N 3
3:
5: 0 Ln
N N 3 m N
n v) N
d
a I
a E x -a I I
X X X X
z? V
8 8 8 8 f 8
N N - N
0 Ln 3 m N N
0 0 0 0 t - L - m m c - L - m m
t - t - m m N N m m 0 m N N N
" -
L x N
t-- L-- x N
s * m N N
a a 3 3
a a P I CI w
X X X rn X
LD
8 8 8 8 8 :
X
8
X X X
8 8 8
lx N
N OD 3
i
-0 I
EN
s" V
X
8
3 N
m
% N
a I
X
lx N
% * m N N
U U a I * I
* m N lx N
s m (D
i 3 m
s 2
rd
a 3
X m m X X
8 8 8 8
OD W t- m
m
EN
8
m
m
E W V
0 *
TABLE 99
(con
td.)
m
m
w
Met
ho
ds of
N.
R
R'
R"
X
syn
thes
is
M. p
. or
B. p
. R
efer
ence
s D
eriv
ativ
es
3H
COOCH,
OH
COOCH,
II dl
M. 232"
159
xv
336, 337
VII
I 159
c- 2%
COOC,H5
II dl
M. 15
1"
159
m m m m m m 3 3 3 3 3 3 OD m m m a m
m m
t - N O W 3 3 N r l N 3
I , I I I 1 a 3 m m N W rl n L - N o w d 3 3 3 N 3
0 . 0 t - ~ n m h
0" I
TA
BL
E 1
00.
Th
iop
yraz
olec
arb
oxyl
ic A
cid
s an
d th
eir
Fu
nct
ion
al D
eriv
ativ
es
TA
BL
E 1
00 (
cont
d.)
a:
,a 0 N.
R
R'
R"
X
M
eth
ods
of
syn
thes
is
M. p
. o
r B
. p.
Ref
eren
ces
Der
ivat
ives
3H
"Z
H5
4H
SC
H,C
OO
H
5H
SC
HzC
HzC
OO
H
6H
SC
H,C
,H,
I C
H,O
H
SCH
,
8 C
,H,
SCH
,
CO
OC
,H,
CO
OC
,H,
CO
OH
CO
OC
H,
CO
OH
CO
OC
,H,
CO
OH
CO
OC
,H,
9 C
,H,
SO,C
H,
CH
3 C
OO
H
10
C
,H,
CH
, C
OO
H
CO
OC
,H,
I d-111
a
Xe
XV
I
XVI
VIII
Xe
VUI
XV
I
VU
I
XV
I
Xe
IV a
VIII
XV
I
VIII
VII a
M.
128-
129
" 59
9
162
913
M. 9
0-91
" 91
3
M.
222-
223"
91
3
M.
182-
183"
91
3
M. 2
13-2
14"
913
M.
167-
168'
91
3
M. 24
4-24
5"
913
M. 1
26.5
-127
" 91
3
913
M. 1
33-1
35"
913
M. 2
15-2
16"
(d.)
91
3
M.
109-
109.
5"
91
3
913
M.
172-
173"
8
1 5
M.
127-
128"
81
5
-HC
1: M
. 169
-171
"
Ag s
alt
:
M.
227-
228"
.HC
1: M
. 14
3-14
6"
K s
alt
: M
. 217
-218
" (d
.)
K s
alt :
M.
215-
216"
(d
.)
.HC
1: M
. 15
8-16
2"
Ag
salt
K s
alt : M
. 30
1-30
3"
TA
BL
E 1
01.
Azo
py
razo
leca
rbo
xy
lic
Aci
ds
and t
hei
r F
un
ctio
nal
Der
iva
tiv
es
d
N.
R
R'
R"
Met
hod
s of
X
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
iva
tiv
es
1H
C6
HS
N
=NC
,H,
H
CO
OH
X
VII
a
M.
196-
197"
(d
.)
619
3 C
fiH,
N=N
C6H
s C
H3
CO
OH
I
a
M. 20
6-20
7"
(d.)
27
2
'6'5
CO
OC
,H,
Ia
M
. 14
8-14
9"
227
C6
H5
C
OO
H
XIV
a
M.
179"
17
1
N.
R
R
~
R"
~~~~
~~~
-~
~
.-
-~ ~~
~~
-~
Met
hod
s of
X
sy
nth
esis
M
.p.
or
B.p
. R
efer
ence
s D
eriv
ati
ves
1H
C
H3
CO
OC
2H5
XIX
d
M. 17
2"
165
C6
H5
N
=NC
,H,
CH
3 C
N
VII
a
M. 13
0"
419
3 D
o.
-
N=N
C6H
5 C
H 3
CO
OH
X
VII
a
M. 2
05"
419
4 C
6H5
N=N
C6H
5 C
6H
5
CN
V
II a
M
. 204
-205
" 41
9
4 0
;
x
e:
842
z N
3
3 0
s N 0 N
L (D 3
W N 3
3
3 CQ
2 2 s 2
rd rd
0 V
k- * E E
x * v) N N
rd
E d
E
m 3 N * 3 3 0 L- 03 m 3
e 3
843
d a l. 0 9
X
L- LD N
P L- 3
cb r 4
2
P
844
0 0 0 l n r n r n N N N
n n
d i ! 8 V
8
5 : 5 : % N N N
m
O N N 3
o ; b
Z ' E '
f 8 8
3 3
* * m r n N N
m m 3
s
8
m 3 N 3
845
c 5 3
U .3 3
a:
L- W L-
3 N n *
Xi u
Lc
846
m 3
N
2
2 z c
c c .3
c
4 m
e:
e:
I I
cr;
cr;
Q ' z
I
m N
848
m W L- W W 3 t- i
t-
W (D t- t- W t- t- W L-
m t- 3 R
W 3 N v) 3
3 Ln I I m
W 3
I t- L-
Q
iZ , I I 2-0
o" Y
n
x V
cn N
5: m
t- N W N
51
co N 4 m 0 m
849
w
850
TA
BL
E 1
04.
Su
bst
itu
ted
Nit
roso
py
razo
les
a)
4-n
itro
so
:xJfR
' I
N.
R
R'
1
2 3 4 5 6 7 8 9 10
11
CH
3 c1
H
CH
3
C6
H5
H
R"
Met
ho
ds
of
syn
thes
is
Ref
eren
ces
M.p
. o
r B
.p.
Dy
-iv
ativ
es
CH
3
OC
2H5
SCH
,
SCH
,
SCH
,
'IjH
5
SeC
H,
SeC
H,
,CH
, -N
,
-$ C
6H
5
CH
3
'6'5 ,CH
3 -
XIX
c
XV
UI e
XIX
c
XM c
xrx
c
XM
C
XIX
c
XM c
XIX
c
XM
C
XIX
C
M. 8
7"
883
M.
( 126
-127
" (d
.)
1058
1-10
0"
(d.)
696
M.
137"
68
3
M. 9
6"
683
720
M. 14
8" (
d.)
686
M.
117.
5"
M.
136"
68
9
M. 9
9"
67 3
M.
135"
69
6
M. 8
9"
699
.HC
1: M. 1
56"
TABLE 1
04 (
con
td.)
~_
__
__
__
~_
__
__
_ - __
_
_ _
__
~
Met
hod
s of
N.
R
R'
R"
S
ynth
esis
M
.p. o
r B
.p .
Ref
eren
ces
Der
ati
ves
12
C,H
, C
H3
F2
H5
-N
''6HS
XM
c
M. 9
8"
699
.HC
1: M
. 14
0" (
d.)
XIX
c
M. 1
51
" 7
18
XM
c
M. 7
3'
699
.HC
1: M
. 1
29
CH,C
,H,
15
C,H
, C
H3
-N:
X
IX
C
M. 7
0"
699
.HC
l:M
1
34
-
'IiH
5
N.
R'
R"
R
16
C,H
, -N
=C(C
H,)C
H=C
(CH
, 1-
17
C,H,
-N(C
H,)C
H=C
HC
&
18
C,H
, -N
(CH
, )C
H=C
(CH
, )c
(r
19
C,H
, -N
(CH
, )C(COOH)=CHCC~
20
C
,H,
-N(C
H, )C(COOH)=C(CH, )C
O-
XM
c
M. 2
30"
(d.)
2
61
XM
c
M.
253"
26
2
XIX
c
M. 2
59"
262
xu( c
M
. 17
4
262
XIX
c
M. 2
55"
262
b)
N-n
itro
so
11“’ “-BI;”
N’ k0
N.
R
R’
R”
Met
ho
ds
01
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ativ
es
1
cI13
2 C
H,
XM
c
M.
40”
XM c
M
. 34”
1058
1058
W
cn
w
TA
BL
E 1
05.
Su
bst
itu
ted
Acy
lpyr
azol
es
N.
R
R'
R
~ ~~
Met
hod
s of
X
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ati
ves
1
2 3 4 5 6 7 8 9 10
11
12
c1
H
H o
r C
H,
H
CH
,
H
CH
,
CH
,
C6H
5
Br
OC
OC
H,
CfiH
5
H
c1
c1
Br
Br
I I 3
H
Br
H
H
C6H
5
H
CH
, o
r H
H
CH
,
H
CH
,
c1
c1
Br
Cfi
H5
OC
OC
H,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
a
CO
CH
,
CO
CH
,
CO
CH
,
CO
CH
,
M. 7
5-7
6"
XX
Ve
M
. 72
-74
"
XX
V e
M
. 34
"
XX
V e
B. 7
7. 5
"/9
XX
V e
M
. 93-
94"
M.
38"
XX
V e
M
. 114
"
XX
V e
XX
V e
M
. 20-
21"
M. 6
2. 5
-63.
5"
B. 2
01-2
02"
XX
V e
M
. 69
-70"
XX
V e
M
. 106
"
XV
III
b
M. 7
5-7
6"
XX
V e
-XX
VI
a
XX
V e
M
. 84
"
79
501,
504
51
50
1
7 39
56
1
739
79
,70
8
79
501
10
28
10
28
10
28
13
C,H
,
14
C,H
,
15
C
,H,
16
C
,H,
17
H
18
C
H,
19
20
21
22
23
24
25
26
m
cn
27
v1
28
CH
3
C,H
, o
r C
1
CH
, o
r H
CH
3
CH
3
OC
OC
,H,
H
CH
,
C6
H5
H
H
H
H
H c1
H
CH
3
H c1
Br
I H
OC
OC
,H,
H
H
NH
CO
C,H
,
CO
CH
,
C?o
c,H
, -N
=CH
-CH
C
OC
H,
"C,H
5
HS
CO
&
OC
H,
H
cocc
1,
c1
CO
C,H
,
c1
C1
or
C,H
,
H o
r C
H,
CH
,
CH
,
C6
H5
H
OC
OC
tiH5
OC
OC
,H,
H
XX
VI
a 10
28
XX
V e
M
. 10
8-10
9"
1028
XX
V e
M
. 16
9"
263
XX
V e
M
. 12
3-12
4"
262
XX
V e
-XX
VI
b M
. 24
2-24
4"
263
XX
V e
XX
V e
XX
V e
XX
V e
XX
V e
XX
V e
XX
V e
XX
V e
XX
V e
-XX
VI
a
M.
53-5
4"
M. 2
6"
B.
302"
B. 2
18-2
20"/
60
M.
90-9
1"
M.
89-9
0"
M. 4
8-49
"
M.
48-4
9"
M. 82
"
M.
181-
182"
M. 1
09"
XX
V e
-XX
VI
a M. 1
28-1
29"
XX
V e
M
. 11
7-11
8"
XX
V e
-XX
VI b M. 17
3"
504
79,7
08
883
79
51
739
739
1028
1060
778,
naz
1028
1062
cv m m
t- W 3
2
d
E x
m t-
m m
I m m
3
3
2
Y
> X x
In
xu 6 v v
m 0 m N
3 LD
b m
I m
3
t- 3
2
m
0
I
X 4
V
G
V
X
k
N m
m t-
b
I m m
v 3
3
2
m > 8
% a , 0 0
I
G
$I
Em V
m m
m m r- t-
LD
m' N 3 3
I I In N M 3
3 i
m 3
N N ( D W N N
m to N
b v
R m
m I " 0 7
A X h i 2 2
N
W N
B " I
X X 5: x x
4
a 1
xm ?.a V V V
t - w m m m W m m - m
39
C,H,
H
-N(CH~)C(CH,)=CHCO-
XX
VI
b
M. 2
42-2
43"
260
40
C,H,
H
-N(CH,)C(COOH)=CHCO-
XX
VI
b
M.
172-
175"
(d
.)
262
41
C,H,
H -N(CH,)CH=C(CH,)CO-
VII
I M
. 19
2-19
4"
262
XX
VI
b
42
C,H,
H
-N(CH,)C(COOH)=C(CH,)C&
XX
VI
h M
. 27
2-27
4"
262
N.
R
R'
R"
X
Met
ho
ds
of
syn
thes
is
M.p
. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
C6HS
CH
3 c1
CHO
XV
U b
M
. 14
2-14
3"
885
Ph
eny
lhy
dra
zon
e:
M.
174"
88
5
Sem
icar
baz
on
e :
XX
III g
M.
214-
215"
CHO
XX
III g
M.
103-
104"
88
5 S
emic
arb
azo
ne :
M.
182"
Gu
any
lhy
dra
- zo
ne.
HN
03
:
M.
204-
205"
C6H5
c1
CH
3
C6
HS
N=NC6Hs
CH3
m
Ln 4
'CiH5
N=NC,H,
CH20C6Hs
COCH,
VII
a M
. 17
9"
COCH,
VII
a
M.
178"
419
p -n
itro
ph
eny
l-
hy
dra
zon
e:
M. 2
22"
Sem
icar
baz
on
e :
M.
193-
194"
419
p-N
itro
ph
eny
l-
hy
dra
zon
e :
M. 21
8-21
9"
m i co
m
i N 3
I 0 N 3
2
d b-
5
f u
$ u
d A I// 9 I
5 m
16
17
18
19
20
21
22
23
24
25
m
26
cn
(D
H5C
6C0
-s
s
b5
SeC
H,
SeC
,H5
SeC
H,C
OO
H
SeC
H,C
,H5
SeC
OC
GH
s
v c2
XX
I f
XX
VI
a
XX
VI
a
XX
VI
a
XX
VI
a
XX
VI
a
XX
I f
XX
b
XX
b
XX
b
*
M. 156”
M. 7
0“
M. 84“
M. 157”
M. 146”
M. 11
1“
M. 141”
M. 125”
M. 201”
M. 78
”
M. 126”
666
666
697
697
697
697
697
697
697
697
697
697
* F
rom
l-p
heny
l-3-methyl-4-benzoylpyrazole-5-selen
ic ac
id b
y tr
eatm
ent
wit
h SO
,, o
r fr
om
bis-[l-phenyl-3-methyl-4-benzoylpyrazolyl-(5)]-
dise
lani
dete
trab
rom
ide by t
reat
men
t w
ith N
aOH
.
TABLE 105 (
cont
d.)
N.
R
R'
R"
Met
ho
ds
of
X
syn
thes
is
M.p
. or
B.
p.
Ref
eren
ces
Der
ivat
ives
27
28
29
30
31
32
33
34
35
C6
H5
C6
H5
'fiH
5
C6
H5
C6
H5
Se0
3H
C
OC
6H
5
OC
OC
6H5
CO
C6
H5
CH
3 c1
C
OC
6H
5
C6
H5
c1
C
OC
6H
5
c1
CO
C6
H5
N(C
H&
H,C
H,)
, C
OC
6H
5
CO
C6
H5
HO
\
c1
XX
I h
XX
V e
XX
VI
a
V b2
XXV e
XX
V e
XX
Ve
v c4
Ix
XM d
XX
Ve
M. 152"
M 157"
M. 88"
B. 245"/15
M. 127"
B. 340-345"/25
M. 70"
M. 144. 5"
M. 164"
M. 110"
697
679,688,785
981
679, 688, 785,
981
679,697
Ph
eny
lhy
dra
zon
e:
442,708
882
M. 176"
882
679
688
708
708
m 0 t-
b t-
i
k
8
m 0 t-
m 0 t-
. b
m m
k 9
+q 0 = o
Y I
m 0 t-
0 0 * 2-
$ 0
$ a
il
f$ 0
8 G G G G G
86 1
cd d r n d w w w m w o ( D m m 3 n N
r3 t- 3
9
- F - F d a m - 3 * * * 3
0
XW V
X 0
m
Ew X
N n
g g m m N N 2 %
rd
F cd
a x I X : g
5: !-
X m
D.7 8
8 8 8
(D Ln
r d d
W W W W m m
b w * i
50 5-
0 d 0 J
3 N
m m m m W W
m W W
W 3 *
rd
m W co
N r- 3
2
Q
m W N
i
8 %- " 5
Ln
wz- I 1 /
W
863
'H93H
3=N
H 3
OSH
N-
OS=
N
'H'303H
N
F9
Z
VH
~)
H~
~H
H~
~~
HN
c~
~3
~~
'H93H
NS
3HN
'Hg3H
N03H
N
'HN
O~
HN
OH
3HN
HO
N=
N
ZH
N
'H
~O
~H
N
"H
N
'H'3H
3-N
EH
3
JH
I3
13
13
13
'H3
9
HS
'H93 P
'H93 E
'H3
'H93
Z
EH
3 H
I
X
..n
.H
n .N
N(C
H$
~
XX
VI
a
M. 55-56"
B.1
22-1
26"
/1, 5
M. 64-65'
B. 154-156"/2
M. 1Y
596
596
OC
HZ
CsH
5 xx
vl a
xxV
I a
596
10
CH
, xx
vl a
M. 10
0"
596
NH
CO
C6H
5
NH
CO
C6H
,
NH
SO,C
,H,
XX
VI
a-b
XX
VI a-b
XX
vl
a-b
M. 176-
M. 18
8'
M. 17
1"
69 5
116
895
13
C6H
5
14
C6H
5 N
(CO
CH
,),
XX
VI
a-b
-Vm
M. 134.5-135. 5'
484
XX
VI
a-b
M. 193'
695
XX
vl a-b
XX
llI
c
XX
Vl
b
XX
VI
b
XX
vl b
XX
VI
a-b
XX
W a
-b
M. 159"
Oil
M. 99"
M. 163-164'
M. 11
5-
M. 109-110-
M. 153-154"
M. 122-123"
69 5
1096
1096
1096
1098
1096
1096
1098
.HC
I :
M. 183-184-
OC
OO
CH
,
OC
OC
H,C
H(C
H3)
2
FJr I
-C€O
CH
CH
(CH
,),
OC
OC
,H,
21
C,H
,
22
C6H
5
23
C6H
5
%
24
C,H
,
-NH
CO
CH
CH
(CH
,),
NH
CO
C,H
,
XX
vl a
-b
XX
VI
a-b
XX
IU b
-XX
VIb
XX
VI b
M. 114-116"
M. 196'
M 230"
M 167-168"
1098
46
1096
1096
4C
H2
CO
NH
-
--O
CH
~C
ON
(CH
,~
* F
rom
l-p
heny
l-3-
methyl
-4-a
mino
-B-e
thox
y-py
raza
le
by
trea
tmen
t w
ith
form
alde
hyde
and
HC
N
c
9
I
m
Q -
!
! I
L d $ 2 2 r" r" u u u
P
d j
867
t- 2 4
r r * * 3 3 4 3
s
5 5
m m m m
G G G G x M M M M
868
m m 3 2 N
3 3 m v ) ( 0 -
3 In (0
N v) v) 3 3 3 3 3 - 3 + r w co m v ) l n l n v ) r n r n l n w (D w w w w w iD w w w
d 3 3 v) m u ? w w ( D
0" 2"
@ a m 3 3
0 3 m 3 d
869
N N
W W w w w w w v) I ( 3 3 “ N L n m m v ) m i m i m w
4 2
1 1
a i o
c) S
ub
stit
ute
d T
hio
py
razo
les
not
com
pri
sed
in
th
e p
rece
din
g t
able
s
N.
Co
mp
ou
nd
s M
eth
od
s of
sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
-
XIX
a
M. 1
07"
655
1
IV c
M
17
9"
649
XX
VI
a
M.
190"
69
2
* CD * m Ln (D
m v) (0
l l
N m
m 4
P
TA
BL
E 1
09 (
con
td.)
N.
R
R'
R"
BI
Br
N=N
C,H
,
N=
NC
6H5
N=
NC
,H5
X
OC
OC
,Hs
OH
OC
H,
OC
2H5
OC
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6H5
OC
H,
OC
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Met
hod
s of
sy
nth
esis
XTX
a
XX
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a
* XX
VI
a
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a
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XX
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a
XX
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a
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B.p
R
rfer
ence
s D
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M. 7
8"
M.
142"
M.
80"
M.
137'
M.
119"
M. 82
. 5
785
785
509
La
cto
ne
47
281
281
46
47
281
M. 98'
M.
204"
281
281
9 C
6H5
(CH
OH
),C
H,O
H
N=N
CsH
5 O
CH
, X
XV
I a
M
165-
166"
79
9
N=N
CsH
5 oc
n,
XX
VI
a M
. 12
1-12
3"
484
10
C6H
S 73-
484
M. 15
4-15
5"
l1
'6jH
S
N=N
C,H
, O
CO
CH
, X
XV
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N=N
C,H
, O
CH
, XXVI e
M. 12
2- 1
23"
484
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l
c) S
ubst
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zole
s no
t C
om
pri
sed
in t
he
Pre
ced
ing
Tab
les
N.
Com
poun
ds
Met
hods
of
syn
thes
is
XM
d
M.p
. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
M.
122-
125"
M. 9
3"
1059
219
* F
rom
1,4-dibromo-3-methylpyrazol
-5-o
ile w
ith
NaO
H.
* * F
rom
1 phe
nyl-
3-me
thyl
-4,5
-dio
xopyrazoline wit
h (I -k
nzo
ylp
hen
ylh
yd
ruin
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dro
chlo
rid
e.
N m W
b 0 3
2
V
k-
3
V
w
% 0 N 0 Q,
2 s
N Q N Q
k- k-
3 8 V
n *
i- n ,-
& A h W O N 3 3 3
G
m m W
- L D 3 z 3
N N P P * *
3 m W
m al 3
a
B
B
T z li z
0
X W V
al
0 3
t-
t- m 3
i
rl m (0 3 m 3 3
N 1 3
( D W t - N t- W m m
tY N N
i
N N 3
i
N P N N e * ?d *
B B G
m
E
Ln
X W V
N 3
A 3
V V
W 3 m - 3
0 3 3
18
C,H
, C
H3
19
C
,H,
CH
3
C"3
c1
V b
2 M
. 15
5-15
6"
651
I V
c8
M
. 12
9"
651
c1
XX
V e
-IX
- M
. 19
1"
V b
2
58
5,7
02
I
N.
R
R'
R"
Met
ho
ds
of R
" sy
nth
esis
M
.p. o
r B
.p.
Ref
eren
ces
Der
ivat
ives
1H
C
6H
5
2 C
,H5
CH
3
'CiH
S c1
C6
H5
c1
C6H
.5
c1
N=
NC
,H,
c1
Br
S0
3H
N=N
C,H
, c1
V b
2 M
. 19
2"
704
XIX
a
M.
255"
70
1
V b
2 M
. 11
5"
652
V b
2 M
. 11
2"
652
65
0,6
52
v
c8
M.
143"
m
-a W
TA
BL
E 110 (
con
td)
m
m 0
N.
R
R'
R"
R
" M
eth
ods
of
R""
X-
syn
thes
is
M.p
. or
B.p
. R
efer
ence
s D
eriv
ati
ves
681
-H,O
: M
. 22
0"
Cfi
"5
2 C
,H,
CH
3 C
H3
N=N
C,H
, c:
1 I
IV c
M. 17
0"
71
2
c1
M
16
4"
71
2
SUBJECT INDEX
The letter trrrt after a page number indicates ?reaction(s)", and the letter "s" indicates "synthesis".
Acetylenic carbonyls, in pyrazole
Acelytenic derivatives, synthesis 16-19
addition to pyrazoles 78-80 in pyrazole synthesis 26-28,
in pyrazoline synthesis 205-6 41, 59-62
Aldehyde arylhydrazoles, in pyra- zole synthesis 23-6
Alkylation of pyrazoles 71-3 Arndt-Eistert synthesis 139 Azomethine imine addition,
in pyrazolidine synthesis 280 in pyrazoline synthesis 205-6
Aziridines, in pyrazoline synthesis 186-7
Buchner-Curtius cyclopropane synthesis 209
Cannizzaro reaction 125 Carbonyls,
a-halo, in pyrazole synthesis
a, p-unsaturated, in pyrazoline synthesis 181-5,
20-23
189-90 Chromic acid oxidation,
of pyrazoles 66-7,70 of pyrazole thioesters 135
Claisen condensation 120 Cyclopropanes, f rom pyrazolines
209-13
Diazoalkanes, in pyrazoline syn-
Diazo compounds, thesis 195-205
Aliphatic, in pyrazole synthesis
26-34,82-3
Diazo compounds-cont. Aliphatic-cont .
in pyrazoline synthesis 195-206
aromatic, in pyrazole synthesis
Diazonium salts, aryl- , in pyrazo-
p-Dicarbonyl, in pyrazole synthe-
Diels-Alder reaction 178, 279 Dipyrazole sulfides 134s
34-5
line synthesis 207
sis 10-16, 33,82
Enamines, in pyrazole synthesis
Epoxides, in pyrazole synthesis
Ethylene imines, in pyrazole syn-
40-41
57-8
thesis 58, 59
Fridel-Crafts reaction 110, 119, 121, 342
ct-Halocarbonyls, in pyrazole syn-
Halovinyl derivatives, in pyrazole
Hydrazides, thiocarbo-, i n pyrazole
Hydrazine and derivatives,
thesis 20-23
synthesis 28-31
synthesis 20-23
in pyrazole synthesis 10-20,
in pyrazolidine synthesis
in pyrazoline synthesis
53-59
282-3
180-195
88 1
Chemistry of Heterocyclic Compounds, Volume 22 Edited by Richard H. Wiley
Copyright 0 1967 by John Wiley & Sons, Ltd.
Subject Index
Hydrazones, in indazole synthesis
Hydrazonic halides, in pyrazole synthesis 35-41
304-5
Indazole, 1-acetyl- 293 acetylation 3 15-6 1-acetyl-3-methyl- 303s acylation 340 3-amino- 299s) 335s, 344s,
3451%) 3481- 5-, 6-, 7-amino- 309r association 293 3-benzyl- 304s bromination 305 3-bromo- 325rs 5-bromo- 325s 7 -bromo-6 -hydroxy- 308r chlorination 324 3-chloro- 324s-5r) 348s 4-chloro- 325rs 5-chloro- 325s chioru-3 -hjidrmy - 301 s 3-cyano- 299s
5,6-dihydroxy- 308r 5,7-dimethyl- 295s 5, 7-dinitro- 300s 3-duryl- 304s 4-fluoro- 300s 3-halo- 305s halogenation 324 2 -hydroxy - 33 5r s 4-hydroxy- 338rs 5-hydroxy- 338rs 6-hydroxy- 308r, 339rs 7-hydroxy- 300s) 339rs 3 -hydroxy - 2 -phenyi - 3-iodo- 325rs, 348s 3-mesityl- 304s 1 -methyl -,
4-Cyano- 343s
302 s, 336s
association 293 reduction 318
bromination 308 reduction 318
2-methyl-,
Indazole-cod. 5-methyl-,
bromination 308 nitration 308
nitration 308, 329 4-nitro- 308r, 328rs-9r 5-nitro- 308s, 329rs
halogenation 308 nomenclature 293-4
6-nitro- 308r, 329rs 5-nitro-1-benzoyl- 304s nitro -3 -bromo-, isomerism
6-nitro-1, 3-diphenyl- 304s 5 -nitro-3 -methyl- 304s 4 -nitro- 1 -phenyl- 320s 4 -nitro-2-phenyl- 303s nitrosation 309 1-phenyl- 320rs-21r 2-phenyl- 321s, 322r
nitration 308 sulfonation 309
292
3-phenyl- 304s, 322-3s, 323-41-
isomerism 291, 323 physical properties 317 reactions 318-9,341,355 reduction 3 18 side-chain acids 343 sulfonation 309 synthesis 295, 299, 300, 317-8 t e t r ahydro - 36 2r s
1H-Indazole 289, 293 2H-Indazole 289,293 3H-Indazole 290, 355-6 Indazole- 3-acetic acid,
bromination 308 reactions 343-4 synthesis 343
Indazolecarboxamides, synthesis
Indazolecarboxylic acids 340-44 Indazole-3 -carboxylic acids,
reactions 325,341-2 synthesis 300,341, 342-3
Indazole -1 -oxides, reactions 354-5 synthesis 304, 353-4
Indazoles 289-365 1-acetyl- 303s
341
882
Subject Index
Indazoles-cont. acylation 315-17 alkyl- 320 alkylation 309-15 amino- 344-51
sulfonation 309 3-amino- 295s) 299s) 344s)
3451- aryl- 303s 1-aryl- 320s 2-aryl- 299s) 301-2s) 321-2s)
3221- 3-aryl- 322-3s arylation 314 2 -aryl- 3 -hydroxy - 302s)
336s) 3371- 3 -aryl-2-hydroxy- 336rs 1-benzyl- 320r halo- 324-8 3-halo- 308s halogenation 305, 308 hydroxy- 309r, 335-40 nitration 308-9 nitro- 328-35,348r nomenclature 293-4 of biochemical interest 352-3 reduced 362-5 ring substitutions 305-17 structure 289-93 sulfonation 309 synthesis 294-305
by N-1, C-3 closure
by N-1, C-7a closure
by N-1, N-2 closure 303-4 classification 294
295-302
304 - 5
tetrahydro- 362s) 363-41- Indazole -4-sulfonic acid, synthesis
Indazole -7 -sulfonic acid, synthe-
Indazolesulfonic acids 351-2 6-substituted 339s
Indazoletriazolene 348 Indazolium halides 314-5 Indazolone,
351
sis, 309
physical properties 352 reactions 358 synthesis 289, 357
Indazolones 356 -61 reactions 358 synthesis 357-8 tautomerism 356 tetrahydro- 363
Indiazene 355 Indiazole 290, 355 Isoindazole 290, 293 Isopyrazole, 3, 4, 4, 5-tetramethyl-,
Isopyrazoles, bromination 86
pyrazoles from 49-52 stability 4 synthesis 28
Isothiopyrones, pyrazole s f r o m
Isoxazoles, pyrazoles f rom 56 64
p-Keto esters , in pyrazole synthe-
Ketomethylene compounds, in
Ketones,
sis 23-6, 33
pyrazole synthesis 33-4
a -epoxy -, in pyrazoline synthe - sis 190
0-substituted, in pyrazoline synthesis 185-6, 190-91
Kishner cyclopropane synthesis 209
Knorr pyrazoline test 179 Kolbe synthesis 339
Malonic derivatives, in pyrazole
Mannich bases 185 Mannich reaction 80 Methyl pyrazole-3,4, 5 - t r i ca r -
synthesis 32-3
boxylate 115
Nitration of pyrazoles 95,96 Nitric oxide oxidation of pyrazoles
Nitriles, a, p-unsaturated, i n py ra -
Nitrosation of pyrazoles 91 Nitrovinyl derivatives, in pyrazole
synthesis 28-31
66
zoline synthesis 185, 191
883
Subject Index
Oxidation, of pyrazoles 65-67 of pyrazolines 215-21
Oxidative cleavage of pyrazole
Oxiranes, in pyrazoline synthesis
Ozone oxidation of pyrazoles
ring 70
186-7
67,71
Pe rmanganate oxidation, of pyrazoles 65-6,70,75 of pyrazole thioesters 135 of pyrazolines 106, 216
N-acyl-, isomerism 138-9 5-alkoxy- 16s 3-alkylmercapto- 20s 5-azo- 101s 3 -benzoyl-4-phenyl- 34s 3-benzyl-5-phenyl-4-diazo-
4 -bromo-3 -methyl- 85s 3 -carboxy -5-methyl - 72r 4-chloro-3-methyl- 85s diazo- 105s 3,4-dibenzoyl- 124s 4, 5-dibromo-3-methyl- 85s 1,3-dimethyl- 216s 1, 5-dimethyl- 86r 3, 4-dimethyl- 86r 3, 5-dimethyl- 105r 3, 5-dimethyl-4-amino- 1041- 3, 5 -dimethyl -4 -diazo- 105s 3, 4-dimethyl-5-iodo- 86s 3, 5-dimethyl-4-nitro- 56-7s 1, 3-diphenyl- 45s 3, 5-diphenyl 70r 3(5)-halo- 73r 4-halo- 84-5s halogenation 84-5 hydrogenation 02 hydroxy- 87r 4 -hydroxy - 32s 4-hydroxy-3, 5-dimethyl- 20s 3-iodo-4 -methyl- 85s 4-mercapto- 23s methyl- 30s 1-methyl- 84r
Pyrazole 81-2
105-6r
884
Pyrazole-cod. 3-methyl- 20S, 26s, 85r 4-methyl- 85r 3 -methyl-4-o -arninophenyl-
54s 3-methyl-1, 5-diphenyl- 11s 1-methyl-5-phenyl- 18s 3( 5) -methyl-4 -phenyl - 2 17s 3-nitro- 35s 1 -p -nitropheny1-5-phenyl- 13s 3 -nitro- 5-P-pyridyl- 701- oxidation 82 1-phenyl- 62s) 135r
bromination 87 reduction 68,70-71
1 -phenyl-3, 5-dimethyl- 68r 1-phenyl-3-methyl- 12s) 701- 1 -phenyl-5-methyl- 12s phenylthienyl- 96r physical properties 81,82 pyrazolo[ 3,4-d] - 106s reduction 70 sal t formation 81-2 synthesis 30, 57,81,216 tautomers 4 tetrahydro- -see Pyrazolidine 1, 3, 4, 5-tetramethyl- 77s)
thioesters 135r 1-p-tolyl- 45s) 68r, 70-71r 1, 3,4-trtiodo- 85s trimethyl- 1061- 1, 3, 5-trimethyl- 77s 3, 4, 5-trimethyl- 53s) 1121- trimethylamino- 106s 3, 4, 5-trimethyl-1-phenyl-
Pyrazole -4-aldehydes, synthesis
Pyrazole -5-aldehydes, synthesis
Pyrazole azo dyes, from pyrazo-
Pyrazole -4 -carbony1 chlorides,
86r
217s
122
123
lines 216
Friedel-Crafts reaction 121
106-17 Pyrazolecarboxylic acids
effect of heat 115 from 2-pyrazolines 216
Subject Index
Pyrazolecarboxylic acids-cont. physical properties 114-5 reactions 114-7
Pyrozole- 1-carboxylic acids, syn- thesis 113-4
Pyrazole -3 -carboxylic acids, effect of heat 115-6 synthesis 56, 84, 106-7
Pyrazole -4 -carboxylic acids, effect of heat 115 synthesis 84, 107-8
Pyrazole -5-carboxylic acids, syn-
Pyrazole-3-carboxylic es ters ,
Pyrazole-4-carboxylic es ters ,
3,4-Pyrazoledialdehyde, synthesis
Pyrazolediazonium sa l t s 104-6 Pyrazole -3,4-dicarboxylic acids,
thesis 109
Claisen condensation 120
synthesis 23
124
1 -phenyl- 1161- synthesis 109-10
4-methyl- 112s 1-phenyl- 115r, 1161- synthesis 11 1-12
Pyrazole -3, 5-dicarboxylic acids,
Pyrazole-4, 5-dicarboxylic acids, synthesis 110-11
Pyrazole disulfones, synthesis 135
Pyrazolenine, stability 4 Pyrazoles 3 - 139
3-acetyl- 119s acyl- 125-61- 1-acyl- 12s 3-acyl- 117-21s 4-acyl- 121-3s 5-acyl- 123-4s N-acyl- 137-39s, 139-40r 3-acyl-1-aryl- 120s 4 -acyl - 5-acyloxy- 1 2 2 s acyloxy - 128 - 30s acylseleno- 132s acylthio 132 alkoxy 1.31-21- 5-alkoxy- 130s alkyl- 82-3s
metalation 83-4 salt formation 83 stability 83
Pyrazoles- cont. 1 -alkyl- 109r 4-alkyl- 40s) 41s alkylamino- 104s alkylation 71-3, 78-80 alkylmercapto- 133s, 133-4r a1 kylthio- 132 -4s amino- 56s, 102-6 3-amino- 98r, 103 4-amino- 103s 5-amino- 36s) 56s, 103. aminoalkyl- 104 aminoarylamino- 103s aryl- 82-3s
metalation 83-4 salt formation 83 stability 83
1-aryl- 57s arylazo- 98s 4-arylazo- 20s) 104 N-arylsulf onyl- 140 azo- 101-2r, 103r 3-azo- 98-9s 4-azo- 99-100s N-benzyl- 76-71- 4-bromo- 89s) 90r, 91r, 107r 5-bromo- 89s carbonyl derivatives 117-26 4 -carboxy - 5-carboxy- 109s chemistry 81-140 5-chloro-4-hydroxy- 128s 4-chloromethyl- 1231-
de a1 ky lation 7 3 - 8 3, 5-diacetyl- 124s diaryl-, spectra 9 dihydro- -see Pyrazolines dimethyl- 10-11s) l l l r 3,4-dinitro- 97r 1,4-dinitro-3-methyl- 95s 1, 3-diphenyl- 45s 1, 5-diphenyl-3-methyl- 68r 1 , 3 -diphenyl-5 -methyl- 68r general reactions 65-80 halo- 84-91 4-halo- 1071- hydrazo- 102s hydroxy- 126-32 1-hydroxymethyl- 741- imino- 102
1 lor, 11 5 r
4-CyaO- 90s
885
Subject Index
Pyrazole s-cont . isomerism 6 -9 naturally occurring 3 nitration 95-6 nitro- 93-7s) 97r, 103r 3-nitro- 93-4s 4-nitro- 66s) 90s N-nitro- 95s nitroso- 91-2s
chemical properties 92-3 oxidation 66, 92, 97 physical properties 92 reduction 93,97,103
oxidation 65-7 phenyl- 57s) 95-61- polyacyl- 124-5 reduction,
to pyrazolidines 281 t o pyrazolines 206-7
ring cleavage 70-71 ring reduction 67-70 selenium derivatives 137 sulfonation 13 5 sulfur derivatives 132-7 synthesis,
by 4,5 ring closure 19-20 from acetylenic carbonyls
with hydrazines 16-19 from aldehyde arylhydra-
zones with p-keto e s t e r s
f rom diazo compounds
from /3-dicarbonyls with hydrazines 10-16
from epoxides and ethylene imines 57-9
from a-halocarbonyls with thiocarbohydrazides
f rom heterocyclic com -
f rom hydrazonic halides
f rom isopyrazoles 49-52 from pyrazolines 41-9,
f rom pyrazolones 62-3 from syndones 59-62 from 1, 2, 3, -tricarbonyls
with hydrazines 20
23-6
26-35
20-23
pounds 53-7
35-41
52-3, 215-17, 219
886
Pyrazoles- cont. tautomerism 4-6 trichloromethyl- 106r 1,3,5-triphenyl- 68r N-unsubstituted 78-91-
Pyrazolesulfinic acids 136 Pyrazolesulfonamide, synthesis
Pyrazole-3(5)-sulfonic acid 216 Pyrazolesulf onic acids,
reactions 136 synthesis 135-6
216
Pyrazole sulfones, synthesis 135 Pyrazole sulf oxide s, synthesis
135 Pyrazolethiones,
oxidation 135 pyrazoles from 62-5,133
Pyrazole-3,4,5-tricarboxylic
Pyrazolidine, acids, synthesis 112-13
3,5-dimethyl- 281s 1,2-diphenyl- 282s) 283s perfluoro- 283s 1 -phenyl- 283s 1 -phenyi-4 -allyl- 283s 1 -phenyl-4-hydroxy- 283s 1 -phenyl-3 -methyl- 281s 3 -phenyl- 5-styryl- 281s physical properties 279 synthesis 282
Pyrazolidines 279-84 chemistry 284 oxidation 207 synthesis,
by ring fusion 279-80 by reduction 69,70, 281 by cyclizations 281, 282-3
Py r azolidone s) pyrazoles from 63 synthesis 216, 223
1,2 -dimethyl-5 -phenyl 2811- history 179 5-hydroxy- 52s oxidation 2 15 3(5) -phenyl- 194 -5s reactions 221-3 stability in air 209, 221 synthesis 178
Pyrazoline,
Subject Index
1 -Pyrazoline, 3,4-dibenzoyl- 298s perfluoro- 283
1-aryl- 181s 3,3' -bis- 1 -phenyl-, spectrum
2 24 4 -n-butoxy - 205s 5-carbethoxy-3-phenyl- 215r 3 -carbomet hoxy - 3,4-dibenzoyl- 198s 3,4 -dicarbomethoxy 196 1,5-dimethyl- 191s, 216r 1,3-dimethyl-4-bromo- 191s 1,5-diphenyl- 180s ~
1,5-diphenyl-3 -methyl- 206s 4-hydroxy- 186s 5-methyl- 2141- 1-phenyl- 181s, 182s, 222-31-
2-Pyrazoline,
2 12 - 13r
nitrosation 221 oxidation 215, 220
3-phenyl- 183r, 205s rearrangement 222
5-phenyl- 189s isomerization 214 rearrangement 2 2 2
1 -phenyl- 3 -methyl- 182s, 206s, 2201-
1 -phenyl-5-methyl- 182s, 215r
synthesis 70, 204 1-o-tolyl- 2211- 3,5,5-triethyl- 2161- 3,5,5-trimethyl- 2221- 1,3,5-triphenyl- 185s, 2151.
Pyrazolinecarboxylic acids, oxida-
Pyrazoline diazoketones, synthesis
Pyrazoline -3, 5-dicarboxylates,
Pyrazoline-N-oxides 207, 220 Py razoline s
tion 106
204
.. oxidation 11 1
177 - 26 7 acyl- 1201- alkyl- 1061- chemistry 209-25 history 179 4 -hydroxy 57s isomerism 178 oxidation 215-21
to pyrazoles 41-9
Pyrazolines-cont. pyrolysis 209-14 2-pyrones from 213 reduction to pyrazolidines
28 1 reductive cleavage 221 spectra 223-5 synthesis,
cyclization based 192 from aliphatic diazo corn - from aliphatic hydrazines
from arylhydrazines
from pyrazoles 68-71,
from pyrazolidines 207 miscellaneous 206-8
po)i"ds 195-206
189-92
181-9
206-7
taut ome ri sm uses 225
cyclopropanes from 209 fused-ring 207s ' isomerization 198-200, 202 N elimination 210 oxidation 220 spectra 223 synthesis 178, 204 tautomerism 197-8, 211
acetylation 221 alkylation 221-2 l-alkyl-2-phenyl-, spec t r a
224 3-amino- 223s 1H-3-amino- 191s 1-aryl- 2201- 1 -aryl-3-amino- 185s 1 -aryl-3-arylazo- 207s benzoylation 221 bicyclic 190s bis- 220 1 -carbamyl- 190s
spectra 223 3-carboalkoxy-, spectra 224 cyclopropanes f rom 209 1 -( 2,4 -dinitropheny 1) -
5, 5-diphenyl- 205s 1H-4-hgdroxy- 191s
1 7 7 - 8, 2 14 - 1 5
1 -Pyrazolines,
2 -Pyrazolines,
183-4s
887
Subject Index
2-Pyrazolines- cont. 3-methyl- 223 nitrosation 221 1-nitroso- 221r oxidation 216 4-phenylazo- 222-3 1-phenyl-4-hydroxy- 186s 1 -phenyl- 5-hydroxy- 2171- 1 -phenyl-5-substituted 2231- pyrazoles from 216 reactions,
a t position 1 221-2 a t position 3 222-3
spectra 223-4 synthesis 68, 178 tautomerism 211 1, 3, 5-triaryl-,
flourescence 224-5 spectra 224
3-Pyrazolines 178-9 spectra 224 synthesis 194-9, 205
oxidation 216 2 -Pyrazoline -3 -sulfonate, n -butyl-,
Pyrazolium salts, alky lm e r capto - amino- 104r 5-chloro- 104 dealkylation 75-6,77-8 3(5)-halo- 136r reduction 69 reductive cleavage 71 synthesis from pyrazolones
1 3 3 - 4 r
72 5 -PyrazoIone,
3-phenyl- 129r, 130r 1 -phenyl- 3 -methyl-
alkylation 130 imino-, tautomerism 104-5 oxidative cleavage 220-21
28 1 r Pyrazolones,
Pyrazolones- cont. pyrazoles from 62-4,87-8 reduction to pyrazolidines
synthesis 16, 36 thio- 132r
28 1
Pyrazolyl alcohols, oxidation 67
Pyrones, f rom pyrazolines 213 pyrazoles from 54, 55
Reduction of the pyrazole ring
Reductive cleavage, 67-70
of pyrazolines 221 of the pyrazole ring 70-71
Rosenmund reduction 119, 122, 123, 124
Sandmeyer reaction 87, 106,324,
Semidine rearrangement 103
Skraup synthesis 104 Sommelet reaction 123 Sulfa drugs 345-50 Syndones, pyrazoles from 59-62
343
Thiocarbohydrazides, pyrazoles f rom 20-23
Thiopyrones, pyrazoles from 64 o -Toluidines, indazoles from
1, 2, 3-Tricarbonyls, pyrazoles 295-8, 299-300
from 20
Willgerodt reaction 108
888
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