ADDITION REACTIONS OP SOME

AROMATIC ALDAZINSS

APPROVE© j

fa3^r2f^rarior

or rroreaaor

Qctor Department of'^hwaistpy

ADDITION REACTIONS OP SOMB

AH0MATIO ALDAZINKS

VB»XS

Presented to the Graduate Cotmcll of the

North Texas Stat# Collage In Partial

Fulfillment of the Requirements

For Mi© Degree of

MASTER OF SCIENCE

BY

Stewart OfDell, B« S» in Ghexaistry

Denton, Texas

August, 1954

TABLE OP CONTENTS

LIST Of TABLES ±T

Chapter

I, Xffl0©t?CTI01 . 1

II. ' SXFgRIMMTAL 6

III. DISCUSSION 15

BIBLIOGRAPHY . . . . 19

ill

LIST OF TABLES

fable Pag#

1* Fractionation Ranges and Results 13

lv

CHAPTjBR I

IHTROD::CTIOH

Certain hydrocarbon diene systems hava long boon known

to undergo 1,4 addition with a number of reagents giving

rise to cyclic compounds • In 1917, Bailey and Moore-*- reported

encountering an unusual addition of cyanic acid to benzal-

azine. This nitrogen containing diene system underwent addi-

tion of two moles of cyanic acid in glacial acetic acid at

low temperature. The resulting compound was investigated

with regard to its structure by means of hydrolytic degra-

dation; on© of the degradation products which corresponded

to a loss of one mole of cyanic acid from the original addi-

tion compound would not add cyanic acid to regenerate the

original compound, nor could an intermediate indicating addi-

tion of one mole of cyanic acid to the diene be isolated.

The conclusion was that the addition compound was bicyclic,

and that the addition of each of the two moles of cyanic acid

was dependent upon the other. The structural formula (I)

— c = o I I I p

0=C Jh-H

^ \!6TT5

(1) J. ft. Bailey and N. H. Moore, J. Am. Chom. 3oc., 30, 279 (1917). ~

was advanced with the name 5,41 -diketo-3,5 ̂ diphenyl-hexa*-

hydro«-l#2-triasolotriazole for the products Also, In 1917,

Bailey and McPherson^ proposed the nam® "criss-cross" for

the l,3-2#4 addltl&& reaction*

The outstanding feature of the reaction Is the simul-

taneous addition of two moles of cyanic acid to the aslne,

since one laol© cannot add 1,5 without another adding 2S4 at

tdie same time.

Bailey and MeFherson5 reported similar additions of

phenyl isocyanate to aromatic aldazlnes in sealed tubes at

elevated temperatures• The product obtained from benzalazine

and phenyl isocyanate was 5,5}~diketo~3»4y4',5 '-tetraphenyl-

tetrahydro~l,2~trialolotrlazole • The »~nitrobenxalazine, •

cinnaaalazlne, and furfuralazine analogs were reported* to'

addition of thiocyanlc acid to some aromatic aldazines waa

also reported which waa similar to that of cyanic add, and

the products were found to be base~soluble indicating a mer~

cap to group* These compounds were thought to be of the tri-

azolotriazole type.

Butt and Guha* reported the addition in glacial acetic

acid below ten degrees centigrade of two moles of cyanic add

to hydroaromatic ketazines • The structure was Indicated to

{2) J. R* Bailey and A* T* MePherson, J* Am* Ohm.* So©** §9, 1388 (1917).

<3) Ibid.

(4) D* B* Dutt and P. C. Guha, Current Sci« (India), 18, 297 (1949)f £» A., 4S, 614a (1951). ' ' "**

he of t: q trlasolotriasole by hydrolytic degradation .

Keactioos with the ketasinos of cyclollexanone, 2-snethyl cyclo-

hexanone* and 4-jaethyl cyelohexsnone were listed, ilydroaro-

siatic ketazi* ea wero also r e p o r t e d to roact sr l th th a ©cyanic

a.eld; the str ;cture of th® product was undot eraln©d.

«iyatake& effected tho ad lit ion of thlocyariic acid to

some aliphatic ketazines in acetic acid by heating the reaction

mixture* Acetone, 2-butanon©, and 4~heptanone kotaziaQa were

employed .

In an investigation Into soif.e polymerizations i'Ueodor

.a^ner-Jauregg^ found t ̂ at benzalazii ;© reacted v/i th two i.ioles

of raalelc anhydride ia pafluxing beazane • Tho saria product

was -roduced vhen the sol von t was omitted and the reactants

aixed In fe,@ molten state# <Vagner~J&ur ©gc< suggested that

the reaction involved a 1,3-2,4 addition to produce 1,2,3,5,6,7-

hexahydro-3 ,7-diphenylpyrazolo (1.2 )pyrazol~l, 2,5,6-tetraoar-

boxylic dianhydride (XI). two nolo© of diaethyl naloate

added similarly*

V * ' H

\ / 0. ? ? ,0 j c — c it c — c '

< * 1 1 > ,C—C N. .C— c f

0' H . 0 ^ H \ X I / \ H C6H5

J

(5) K • Miyataka. J . tfharm. 3oc. Japan. 73 , 460 (1953): t- • A., 48, 5145c (19547 . ~

""WW? 16) X . -.vainer ~Jaure£-;# Bar#. 63B> 3213 (1U30).

4

Alpen,7 in dealing with the reaction of naleic anhydride

aiii benzalazine, isolated a 1:1 adduct tot found that the ad-

duct did not react with, additional maleic anhydride to form

II* Compound II dissolved in sodium hydroxide solution hydro-

lyzed to the corresponding tetracarboxylic acid which was pre-J

cipitated upon neutralisation of the solution* The anisole

aldazin© analog was also prepared and exhibited similar be-.

havior*

Dutt and Guha® prepared the cyclohexanone analog of II

by reacting cyclohexanone ketazine with msleic anhydride in

dry benzene; with moist ether as a solvent, the product of

the reaction was maleic acid cyclohexyl 1 denemonohydr azid©.

The reaction of •; azines - w i t h malele anhydride in the

presence of traces of moisture was Investigated by Caronna.9'*0

Guminalazin© and bensalazlne reacted with maleic anhydride

in toluene to give maleic acid cuminylidenemonhydrazi de and

maleic acid benzylideneaaonohydrazide, respectively* - The mono*

nitrobenzalazines were found not to react under the conditions

easployed. The reaction occurred neither in toluene dried over

sodium metal, mn* in the presence of excessive moisture* Ace-\

tone and 5-pentanone ketazine® underwent the reaction faster

(7) J* van Alpen. Rec. trav* chlm.. 6i#. 80S (1942)I Cham* Zentr*. 1943. II, 1799| C. A., 58, H24© <1944)*

(8) Dutt and Guha, £* Indian Chem* Soc., 27, 151 (I960)} £• A*> 1526i (1951). •' •"*

(9) G. Carrona, Oazz* chiia* ital*, 77, 427 (1947)J C. A., H # 55471 (1948). •' ""

(10) Ibid.. 77, 482 (1947); £. A. Jtg, 5548f (1948)*

than did propiophenone katazine • Benxophenone ketazine did

not react*

Thios ealearbazones w s reported as products in the re-

actions of some Mines with thiocyanic acid.11 In some cases

the thios eaicarbasones vere formed to the exclusion of other

products•

(11) Hiyatake, $&* cit.

CHAPT5K II '

mtmmwTM,

- Preparation of Benaalazine

A solution of 29.4 al. C0,5 mole) of hydrazine hydrate

(85^) to 100 ml, of water was placed In a 500 sal. flask# To

this solution was added 10 ml, of concentrated sulfuric aeid

and 105 g* CI mole) of benzaldehyde• The flask was then

shaken vigorously for 1© minutes j the flask became very hot«

Intermittent shaking was continued until the flask became

cool, and a very heavy precipitate had formed. The solid

w m filtered off and reerys talllzed from methanol • The yield

was 56,5 g. (54 .l£) of bright yellow needles, sup. 92-95°.1

T h e reaction was found to proceed well when an equivalent

amount of hydrazine sulfate was substituted for the hydrazine

hydrate and the addition of sulfuric aeid emitted* The gen-

eral scheme of this preparation was used to prepare the azines

of several aromatic aldehydes*

Preparation of 4-Ben*oxybenj5alaxine

The product was a light yellow powder, sup. 227-229°,

teal, Calod« for C28Fg004N2j N, 6.24. Pound: N, 6,30,

Preparation of 4-DiethylaBtinobenzalazlne

CD All melting points are corrected,

An orange powder was obtained, aup« 184-185° •

Anal. Calcd. f o r Cg2%#4* M> 16 •OU Found: 1 , 15.97.

Preparat ion of S»Stfooxy«»4-hydroxybenRal as ine

4 yellow powder mealting a t 209*210° was obta ined.

Anal* , Calcd. f o r Gie^O 0 #®* R» B * m * P o u n d * H» 8 » 4 5 *

Preparat ion of 5 ,3 ' - D i k e t o - S ^ , - b i s (2»methoxy~ phenyl) •hexahydb?©*! ,2-tri»2©l0tria&©l ©

To 2*68 g . (0.01 mole) of 2-aothoxybenzalastina in 20 ml.

of g l a c i a l a ce t i c acid ware added 4 .0 g . potassium cyenat®

In small p o r t i o n s . The mixture was allowed t o s t and , with

occasional shaking, f o r two days. Water was .added and the

so l id f i l t e r e d o f f . The y i e l d , a f t e r r e c r y s t a l l i s a t i o n from

dioxane, was 1 .2 g . (33.9JO of f i n e white needles , m.p. 221.8-

222.5°. . Anal. Calcd. f o r 15»HI. Pounds N, 15.78.

Preparat ion of 5 ,3 ,~Dimercapto-'3,5 *-bis{2-methoxyphenyl)-dihydro-1, 2~triaj6olotr ia*ole

l i n e grans of potassium thiooysnate dissolved i n SO ml.

of hot ace t i c acid were added to 50 ml. of hot a ce t i e acid

containing 5.3© g . (0.02 mole) of g^ethoxybenaalaz ine . A

heavy p r e c i p i t a t e formed r ap id ly ; the mixture was allowed t o

stand overnight and then f i l t e r e d . The y i e l d , a f t e r r ec rys -

t a l l i z a t i o a from dioxane and water , 4 . 8 g . ( 6 2 * ^ ) of watted

white © r a t a l s , s u p . 195.5*194•§0-:«d©Q»

Anal. Calcd. f o r C18H18°2R4'H2°5 N* 1 3 « 8 7 ' P o u n d l N» 15.96.

8

Preparation of 5,3f -Dim©reapto-5 ,51 -bis {2-e thoxypheny 1)-

dlhydro-1,2-triasolotrlasole

Mine grass of potassium thiocyanate dissolved in 30 ml,

of hot acetic aoid were added to 50 nl. of hot acetic acid

containing 5.92 g. (0,02 mole) of 2-ethoxybensalaasine. A

heavy precipitate formed rapidlyj the mixture was allowed to

stand overnight and then filtered* The yield, after recrys-

tallisation froot dioxane and water, was 4*25 g# (51.4$) of

fine white needles, m.p. 189.5-190.5° dee. Anal. Calcd. for C20n22°^AS2t H* Foundt 8, 13.43.

Preparation of 5,3,-Biaercapto-3,5'-bis(2,3-dimethoxyphenyl )-

dihydro-1,2-triazolotrlazole

To 3.28 g. (0*01 mole) of 2,3-dimethoxybensalazine in

20 ml. of glacial acetic acid was added 4»S g. of potassium.

thiocyanate with stirring. The mixture was allowed to atand

for two days and was stirred occasionally} ̂ the precipitate

was filtered off and reisry&tsllized from dloxane and water,

lb® yield was 2.7 g, of white translucent crystals; neglect-

ing hydration, the yield was 60.7$. The compound melted at

191.5-193° after it was dried at 135° under vacuum.

Anal. Calcd. for C20H22°4N4S2* *» 12.55. Foundx », 12.50.

Preparation of 1 # 2,3 ,5 ,6,7-Hexahydro-3 ,7-diphenylpyrasolo-(1.2 )pyra*ol-1,2,5,6-tetracarboxylie Dianhydride

Twenty-seven and five-tenths grams (0.28 aol«s) of

raaleic anhydride were melted and raised to a temperature of

140° in a 50 ml. beaker. Twenty and eight-tenths grams of

3

benzalazine tin added in small portions, and the moisture

allowed to flash off. The temperature of the reaction mix-

ture was maintained at 135-140°j after a few minutes the

mixture began to thieken rapidly and required cooling in a

water-bath to hold the temperature below 140°* When the

mixture had besom© quite thick, the beaker was placed in a

steam bath for two hours. The resinous reaction product was

then extracted wife three fresh portion# of methanol and then

with ether. The remaining white powder was filtered and

dried* The melting point of the crude product was 290° uncor.

A small portion was r©crystallized from acetic anhydride and

taken for analysis; this sample melted at 296-298°dec. The

yield of crude material was 10.0 g. (24.8$).

teal. 0aled. for N, 6.93. Found: lt 6.96*

Preparation of l,2,3,5,6,7-Hexahydro-3,7-bis(2~methoxyphenyl)-pyrasolo(1.2)pyrasol-l,2,5,6-tetracarboxylic Dianhydride

Seven grams of maleic anhydride war® heated to a tem-

perature of 125° In a 50 ml. beaker. To this were added

slowly 8.04 g. (0*03 mole) of 2-methoxybenxalasine. The addi-

tion required about five minutes; heating was continued at

the same temperature until a light-colored precipitate had

formed. When the reaction appeared to be complete, the mass

was extracted with three fresh portions of bensene, then with

ether, and then with methanol. The remaining whit® powder

was filtered and drl#d, m.p. 280-282° dee. fh® yield was

2.68 g. 0L9.5jg).

10

Anal. Calcd. for C24H20°8B2* 5* 6«04* pourxdi N, 6.07.

Preparation of l,2,3,5,6,7-Hexahydro-5,7-bls(2-ethoxyphenyl)-

pyraj2ol0Cl.2}pyrmz0l-lf2,ll-,6«t»tr4^srb©xylie Dianhydride

' Bmvm- gram of malaic anhydride were heated to a temper-

ature of 125° in a 50 ml. beaker. To this were added slowly

8 .88 g. (0.03 sole) of 2-ethoxybenzalazine. The addition re-

quired about five minutes; heating was continued at the same

temperature mtil a light-colored precipitate had formed.

Shell the reaction appeared to be complete, the mass was ex-

tracted with three fresh portions of bensene9 then with ethey,

and then with methanol• The remaining white powder was fil-

tered and dried, m.p. 288-270°dec. The yield was 5.05 g. (20 . e g ) .

teal. Calcd. for CjjgH^OgHg: N, 5.69. Pound: », 5.88.

Preparation of 1,2,3,5,6,7-Hexahydro-3 t7-bis(2 ,3-dime thoxy-phenyl)pyrazolo(1.2)pyrasol~l,2,5,6-

tetracarboxylle !)ianhydride

Five grams of maleie anhydride were heated to 120° in a

50 ml. beaker. During the slow addition of 6.56 g. (a.02

mole) of 2,3-dimethoxybenealazine to the melt, the tempera-

ture was maintained at 115-120°. When the mixture had become

quite thick, it was extracted with three fresh portions of

benzene and then with ether. The resulting whit® powder was

filtered from the ether and dried, m.p. 205-210° dec. A

small portion of the product was recrystallized from acetic

anhydride| m.p. 207-209° dec.

teal. Calcd. for ̂ 2^L2&°l(?2i K* S*54* Found: I, 5.30.

11

Preparation of Tetramethyl lf 2,3,5,6,7<-Hexahydro~3,7-di phenyl-pyrazolo(l*2)pyrazol-l, 2,5 ,6-tetracarboxylat®

Pour and four-tenths grama (0*01 sols) of 1,2,3,5,6,7-

hexanhydro-3 ,7-diphenylpyrazolo (1 .2)pyraxol-l ,2,5 ,6-tetraoar-

boxylic acid were placed in a 250 ml* flask} to this solid

ware added a*8 g» of diazomethane2 dissolved in 100 ml. of

ether. Th© mixture was allowed to stand 3,5 d&ysf during this

time bubbles evolved slowly from the mixture. When the re-

action appeared to be complete, the solid was filtered off

and washed with 10$ sodium hydroxide solution. The resulting

crude material was placed in 80 ml. of methanol, and the mix-

ture was heated to boiling and filtered* The filtrate was

all wed to stand at room temperature for several days} white

crystals <0*35 g.) were obtained in this way, sup* 230-234°.

This compound was prepared fro® dimethyl maleate and

benzalazine by Wagner-Jauregg, sup* 238-234°.3

Anal. Calcd. for i S, 5.64. Found: 5.69. 26 28 8 2

Beaction of Aniline with 1,2,3,5,6,7-Bexahydr©-3,7-diphenyl-pyrazolo(l.2)pyrasol-l,2,5,67tetracarboxylic Bianhydride

Twenty and two-tenths grams (0.05 mole) of 1,2,3,5,6,7-

hexahydro-3,7-diphenylpyrazolo(l.2)pyraxol-l,2,5,6-tetracar-

boxylic dianhydride, 27.9 g. (0.3 mole) of aniline, and 250

ml. of benzene were placed in a 1-1., three-necked flask

fitted with a stirrer and a distillation head. The flask was

(2) fi» Arodt, Organic Synthesis. Coll. II (1943), p. 165.

<35 T. Wagner-Jauregg, Bj*., WB, 3324 (1930).

12

heated, and the benzen.® was allowed to distill slowly| slow

stirring was employed to minimize bumping* , At the end of nine

hours the flask was allowed to cool, and the solid residue

w m filtered from th® remaining benzene and washed with pe-

troleum other. The solid was then dissolved in 100 ml. of

«odium hydroxide solution; upon the addition of ether this

solution yielded a heavy white precipitate which was filtered

off, washed with ether, and dissolved in water. The water

solution was then acidified to a pH of 5j the resulting pre-

clpltate was recrystallised from methanol, sup. 189-190°.

This product gave a positive snilide test (Tafel) and ©or*

responded in nitrogen content to s. disnilide of the tetracsr**

boxylic compound. . .

Anal. Calod. for %4J%o0©M4s I # 0#49'* P o u n d 5 H» 9*5S*

Treatment of 1,2,3,5,6#7-Hexahydro-3,7-diph@njlpyra2olo (1,2)pp?-azol-1,2,5,6-tetracarboxylic Acid with Sodium end n-Pentanol

A mixture of 44 g. {0.1 mole) of the tetracarboxylie acid

and 300 ml. of n-pent«nol was placed in a. three-necked, 1-1.

flask fitted with a reflux condenser snd a button stirrer.

The mixture was heated to reflux and 74.8 g» of metallic so-

dium were added in small portions. When the addition of the

sodium metal was couplet®, the reaction mixture was allowed

to cool, and ©00 ml. of water were added. The organ!o layer

was separated from the aqueous layer. The water solution was

extracted thoroughly with ether, and the extract was added

to the organic layer. The ether was removed from the alcohol

13

solution "by evaporation. Distillation of the alcohol from'

this solution at reduced pressure left a dark, viscous res-

idue. This residue was subjected to fractional distillation

at 2 mm.; each fraction contained about 0,5 ml* The results

are given below (Table !)•

TABLE 1

FRAC TIOKATI OH RAJJOES AKD RESULTS

Fraction lumber

Teiaperature (°C)

Test Results and Physicals-Properties

1 ... 57-68 2 68-59 Refractive index 2.430, C, I, 5 ' • 5 W 2 S» Vm B» 4 63 Refractive index 1,437, 8 63 6 7 81-88 8 88-90 I. " 9 90-92 Refractive index 1.454,.

10 98*95 11 .• 95-04- • ,

12- • • . 94-95 IS 95-96 14 90-97 • M, P, G» B. 15 97-98 16 98-100 i» c. . . . 17 100 B, B. 18 100 v B»p» 256-257 uncor. It 100-102 dp, gr. 0.387* ref. lnd. 1.472. to im B .p , 358*.

£ indicates negative eerie nitrate test for alcohol groupsT I indicates negative iodoform teat* H indicates negative "qualitative teat for nitrogen* f indicates rapid deeolorisation of pansanganate solution • jf indicates rapid deeoloritatloji of bromine in carbon tetrachloride *

14

Benzole acid, identified m the p~toluldide, precipi-

tated fros fractions 11-14 cm standing, Attempts to hydro-

XIae representative aan^lea in basic solution yielded incon-

clusive results, although soma hydrolysis mm observed. Per-

manganate oxidation of ft portion of fraction 19 yielded ben-

solo acid* A value of 255 was obtained for the nolecular

weight of the last four fraction® by the Cofctrell method»

Practical 18 was soluble in ether, benzene, arid carbon tetra-

chloride and Insoluble in methanol and acetic acid. Hitrie

acid oxidation of a portion of fraction 18 gave a gummy res-

idue which was soluble In methanol -and contained no earbonyl

group. Nitration of a portion of fraction 18 wife nitric

acid In sulfuric acid was not observed. Fraction 16 appar-

ently did not landergo acetylation with acetic anhydride and

anhydrous alwrainm chloride In nitrobenzene.

OHAPfffl III

DISCUS3I0N

Unsuccessful attempts were w d s to raact cyanic acid

sad thiocyanic acid wife 4-hydroxybenzalazine, 2,4-dihydroxy-

benzalazina, 3-athoxy-4-hydroxybenzalazine » 4-methoxybenzal-

axine, 4~benzoxybenzalazine, and 4-diethylamlnobenzalazine.

Cyanic acid was not observed to react with 2-ethoxybenzal-

azine or 2,3-di»ethoxybenzalazlne.

In general, addition to amines presumably Involves an

electromeric shift from the methylene carbon toward the

adjacent nitrogen. If the methylene carbon la attached to

an a ton which decrease# its positive character, the polar-

ization of the double bond Is in effect reduced, and the

reactivity of the azine Is decreased* In substituted aro-

matic aldazlnea the electron deficiency of the methylene

carbon is somewhat offset if the subatituent is in the para

position and is ortho.para-dlrectlng; the effect is much

less if the subatituent is in the ortho position. This line

of reasoning accounts for the lack of reactivity of above

azines which have a hydroxyl or a methoxyl group para to the

azine chain.

Thiosemiearbazide was used to prepare the thiosemi-

carbazone of 2,5-dimethoxybenzaldehyde• The uncorrected

melting point of the compound was 228-229°•

15

16

The procedure of van Alpen was modified in order to

1

Achieve the addition of maleie anhydride to benzalazine*

Slow addition of the asine to the molten anhydride was found

to minimize hydrolytie aide reactions • At temperatures be-

low 150° the addition tended to be sluggish and incomplete;

above 140° decomposition became pronounced» Extraction of

the crude reaction product with methanol was found preferable

to extraction with benzene*

The above general scheme was employed with 2-methoxy-

benaalazine,-2-ethoxybenzalazine, and 2 ,3-dimethoxybenzal-

azine with one notable changef treatment of the product ob-

tained from 2,3-diraethoxybenzalaslne with hot methanol caused

decomposition; it was successfully extracted with benzene

and ether* This compound was observed to decompose when dis-

solved in sodium hydroxide solution* 4-Bydroxyhensal azine,

2,4-dihydroxybenzalazine, 3-ethoxy-4-hydroxybenzalazine,

4-ben2oxyb®nzala2in©, and 4~di©fchyl malnobrnzalazin® showed

no tendency to react with maleie anhydride either by the

above method or in xylene •

1,2,3,5,6 , 7-Hexahydro-3,7-diphenylpyrazolo(1.2)pyrazol-

1,2,5,6-tetracarboxyli c dianhydride was readily converted to

the acid by dissolving it in sodium hydroxide and making the

solution slightly acid with a mineral acid*1 The add was

found to be insoluble in most of the common organic solvents;

(1) J• van Alpen, Rec. trav* chlm., 61, 892 (1942); Cham. Zentr*. 1943, II, 1799; C. A., 38, £?§246 (1944),

17

solution in acetic anhydride converts Mi® acid to the dian-

hydride which, crystallises on standing#

The preparation of functional derivatives of the aeid

was considered one of the most desirable goals of experimen-

tation with the compound• f© this end the preparation of

the aold chloride was attempted! the us#'of thionyl ohloride

and phosphorous pentaohloride repeatedly yielded only gummy

residues, The apparent unavailability of the aold chloride

imposed stringent limitations upon the investigation, partic-

ularly in view of the comparative unreactivity of the parent

dlanhydride•

The dlanhydride was recovered unchanged after it was

heated for long porioda with ethanol and with methanol•

Treatment of the dianhydride with hydrazine under conditions

which gave rise to the cyclic hydraside in the case of maleic

anhydride® produced only the tetracarboacylic acid; the re-

action of aniline with the di anhydride was observed to pro-

duce a dlanilide, however• The only successful esterlfica-

tion of the acid was the preparation of the tetramethyl ester

with dlaxome thane, which proceeded quite smoothly.

Reduction of the tetracarboxylio acid was attempted using

lithium aluminum hydride in ether; the acid was insoluble

(2) W, D. Harris and D«. L» Schoene (United States Rubber Co.), KIP 859 039 (1950) j Methoden der Organisehen Chemie, Vol. VIII, 679 (1962). ' B —

18

in ether, and no reaction was observed to occur during a

period of two weeks# The treatment of the acid with metallic

sodium and n-pentanol failed to produce the desired nitro-

genous products* XHiring the course of the reaction nitrogen

was found to be expelled as ammonia# Ion© of the products

was identified conclusively; it is probable that the benzoic

acid found among the products was formed after the reduction,

perhaps during the distillation# The solubilities of the

higher-boiling fractions indicate that they way contain some

hydrocarbon#

When the dry dianhydride was heated in a distillation

flask, benzaldehyde distilled ©verj awnonla w m also detected

in the vapors from the distillation. The heating of a small

amount of the dianhydride with zinc powder in dlathylene

glycol yielded a small amount of clear liquid, b.p# 855-200°,

The liquid decolorised bromine in carbon tetrachloride; the

odor of this liquid was the same as that of the higher-boiling

fractions obtained by the treatment of the di anhydride with

sodium and n-pentanol.

BIBLIOGRAPHY

Books

A m d t , &*9 "Organic Synthesis," Collectivs Vol, II, He* York* I* ¥#, John W, Wiley and Sons, Inc., 1945,

Mullar, B#, "lethodon A@r Organiaehen Chanie," ¥©1, fill, Stuttgart, Germany, Georg Thierae ?«rl«g# 1952*

Articles

Alpen, J. van, Rec. trav» chlsu, 61, 892 (1942); Chem.

Zentr., 1943, II. 1799; C. AT*38. 88248* (1944).

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1322 (1917), ~ 8 X 8

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