theses and dissertations thesis collection · 2016-07-05 ·...
TRANSCRIPT
Calhoun: The NPS Institutional Archive
Theses and Dissertations Thesis Collection
1946
Guanidine and its nitrogen derivatives
Wishlinski, Thomas J.
Cornell University
http://hdl.handle.net/10945/6420
.
try
U. S. Naval Pc - School
Annapolis, Md.
OUA»I£XK£ AHD ITS XI \& ail\ I
* Theele
Preeented to the Feeulty of the ~raduftte School of "oroell
Unlvereity for the de^re<? of
faster* of ">oi«nee In Hn^lneerln*
mOAUl J. §X88LXlMUt Lff(Jt), US8K
June 20, 19^6
Urn
'.
BIOQftAPHIGAL 3&STCH
The author waa bora in Stevens Point, iBconsIn on
June 5, 1921. He attended elementary school in Berlin,
lsconoln: entered Berlin Hi*rh School and graduated from
tfaara In June, 1938. For a year, ha worked at tha duality
Saua&ga Company, 3erlin, iseonsln aa a meat euttar and
alark. Ha antarod Cantral itate Teachers College, Stevens
Foint, viaconsin, in September, lr09; and received a
Bachelor of Science degree, with majors in Chemistry and
Mathematics and minor in Physios* in May, 1943
•
Ha ment on attire duty in tha H«8« Haral Rmm^rv
Say 31 » 19*35 reported to the U.3. Naval Reserve &id»
shipmen's ">ohool, Kotre r^cme University, South 3entf,
Indiana, "here ha completed the course of instruction and
was commissioned as Snsign *eptember 22 , 19A3« immediately
he reported to the Sub-Chaser Training Center, *ia»l,
Florida, to attend a course in anti-aubmrine warfare.
Upon completion, he reported to the ua;i Harold C. Thomas
(&£ 21) in the Pacific area.
On July 1, 19«5> he reported to the postgraduate
school, ''-'•-• Naval Aaadeny, Annapolis, Maryland, for a
course of instruction in Ordnance Engineering (Explosives).
Ha was selected aa one In a e-roup of fifteen to attend
Cornell University for the oosmletion of the course.
da
M
i M
Of m • -vJs'
« 5fJf
'
ftMPftff* •••
J
Lou 1
n«
Lti t€ i
Mitre
•nit] il ;lno
,
I
.
i
i
IHTKOJXJCTIO*
The lntereat and work on 'i"»nldlne and lta darlv*-
tlvea In the paat deaade haa been jrre^tly atlaulated by
thalr lnerwiael ui*t. | »f lta derlvatlvea, nltr">-
-manldlna la of neoullar lntereat, both technically and
aelentlflcally. a compound la an exploelve and for
thla reaaon many praetleal application* can be found for
It. .nee It «ay be prepared fro» dleyandla^lda, a
derivative of ll»e-nltroren (oalcluts oyanaslde), tha
eaaentlal raw materials for whleh tn nitrogen of tha air
and lleeatone, tha potantlal eupoly la unlimited. It la
Important aelantlfleally, for from It aiclnoruanldlne,
hydra zina, hydronltrla acid, and othar produeta, way ba
obtained from lta reduction, aa an example of tha uae of
thaoa eovoounda, arlnoruanidlne la belnr: dlarotl?ad and
hot-coupled with varloua Interned la tea to furnlah a
whole new aerlea of azo dyea which : oiatis rood dyeliyr
propertlea on animal flbera.
Streaker, In 1861, flrat obtained >~uanldlne aa an
oxidation produot of ruanln*. lnoe that tlce, varloua
en have atudled the propertlee and reactlona of ruanl-
dlne and lta derlvatlvaa. Sore of the more rec-nt work
haa been done by Uavla, whoaa work covered puanldlne,
nltroruanldlne, fruanldlne nitrate, and the olkyl aub-
atltuted c-uanldlnea.
••'
Mi I I
•
'
: I ST
QUAU1VU.
"'uanidlne is an i»ide of urea or the iaidlne of
carbaaele acid. Xn its free state, It occurs only In *
few plants, but its derivatives are widely dletrlbuted.
It occupies a unique position aron* the orranic bases,
for it alone fr^roxipxtes the strong alkalies In basic
strength. Calculations and seneureeents have been »ade
Davit .derfield i6) to show that guanidine is a
strong bate a?xd electrolyte. ?o determine the ratio of
strength of ^unnldonluK hydroxide to that of aodiun
hydroxide, the follow lag teats were used:
(1) Sbaervinp the rate of ehanre of the an^le of
rotation of a hyoseyanine solution in the rrssence of
the two bases.
(2) Relative rates of saponification with ethyl
aeetate.
(3^ I>eprescion of the freefclrvr nolnt of water.
The ratios of puanidoniuas hydroxide to BOdluu hydroxide
obtained were 0.71 ** 1, 0.8* to 1, and 0. . 1,
respectively, alt* the heat of neutralisation of ruani-
dine, 14*19 kilo^raw calorie r>er rras. :ole, w»: lei. Is
only slightly l*es than the constant value for strong
bases. Ouanidlne is a base of the order of strength of
potass iuo hydroxide.
.
>H
W (>o 8o
Cubic Ce»t/ryietz.r5j 0-1 H HCl
Fiq- J
3
Introduction of a single alkyl eubatituant is with-
out nuch effect on lbs basicity of the parent compound.
When two alkyl groups are introduced, the subotance be-
cosec less basic. The introduction of an aronatlo sub-
stliuent also tends to lower the basicity* vis and
ffllderfleld determined the basicity of ^uanidine, of
several of its substituted alky! derivatives, and of
phenyl r;uanidlne. The change of * base with the
•cunt of hydrochloric acid added to it provided a con-
venient means for co^parlns the basicity of those eo»-
the Dure salts of ^uanidlne can be obtained readily.
especially the carbonate which nrystall l""»a well, but the
free base is not easy to prepare. ne nethod used to fiet
the pure eoRommd fro« the salt is to asix an alcoholic
solution of (Puanldlne oerehlorate and potass lu» hydroxide,
resove the insoluble potassiue perchlorate by filtration,
and evaporate the remaining filtrate to dryness in a
vacuus over phosphorus pentoxide* The free base fonts a
colorless, caustic, and very hydroscopic stass of crystals
that aelt indistinctly n.t *>0° ". and deconpose at higher
temperature in a polymerization reaction to forts uela-
mlne. It is stable In aqueous solution and is a mono-
aeid base with basicity as previously described* It foras
stable salts with «eak acids, 10 boric and silicic acids.
The structure of the ruanidln© kation or iruaniflonius)
adiri
:
I
;
Ion haa baan ahown by Uwjhsr and ftraf (17^ to ImM
H.A/--C
*vls # Kallanf* and *% l9) hava ahorm that tha oroton r©
to th« lnida nitro*«m but tha ehar?a aMfta to tha aarbon
atOft* ie forsar aaaaa tha aoat likely eas* , hovav*r t
I ^r^partioa of tha ion. r*y analysis shows
that tha throe nItro*ran atoea are aytraatrloally olaead
around tha earbon ator at a diatanao laaa than th*>t for a
nor»al nitrar«*n-c<.rV>n dovbla bond, la mtat bo baaauoa
all thr** nltropon rtHI "rr f.al:In rt In n reaonanae*
te* the -lo bond enn bo In nil thraa nos«ibla pool-
lion*?, thrae sjtrueturaa eay sartake In tha raaonanaa
hybrid. aaa thrao atruaturas ar«:
+ ,NH* 4WI1, sNHWtf,. W^/> WAt
Tha nropar* ioa of - Ldlna a* <:»rafore t>u« M ona
atructuro alono but to all th rm# atrueturaa In th© hybrid,
nraral synthoaia have boon davolopad for tha x*r*-
paration of guanldina. A»onp thaaa ar«:
(1) Action of aasonia on oarbonyl ohlorida (rboapano),C\ A/H
(2) nation of aaetonla on athyl orthoonrbonate
(3) Saduotlcn of tatranltro^athana
WW
AHWs 4^V\*
MWJ -NAM
••• .'.
O^Yv + \S V*WA* + ^XA 3-V&
WVvHO.
dVvp-c+ jVOA-D-V^Vv «~
t\AV\r + (i >\p)
WWO^Wd -v/uV^^-*- ^NA-O-^W 4 i2**js2 ^ .; -r v
(jpM)1
(a) Edition of awBoni *o oyannmide
A/2 A/-C/V + NH5 + H^N-C
MNH^
(5) \ion of aamonia to chlorooicrin
^nt;?ruction of c^rbontfftrabro' U a with alcoholic
ataaonia In a aealed tube at 100°
LO/y Y- ^/Yyy3 » /6A/-C-A7/W t A/H+Br + 3H Br
(7) Interaction of cyario a«N iodide *lth alcoholic
airaonia in a scaled tube at 100° C
*-c/v *^ > /v/v c/vfwv i j /v/z^ca/ -z&+ /wJJZH(8) Beating a»Roniua thiceyannta- at 170°-1?0° C for
twenty hourr or until hydrogen sulfide no longer
cowrp off. T\H9 yield in thin rroceaa in excellent.NH+NCS ^ A/*,tt4A/CS t=; H^N-C-NH ^ NH^QN t H^S
NHH /VC6 -f KHiQN > H;N- H-NH^ • //A/C S
Only a few of the ayntheeea are on commercial importance;
the othero are aserely laboratory »ethoda.
The process involving the uee of aeaonlua; thioeyanate,
which ia eventually converted to ^uanldine thioeyanate,
»ae for uany years the eaaleat and aoat coawton method for
the preparation of «uanldlne salta. direet nitration
of the ealts, nitroruanidine could be oranared. However,
the nitroruanidine prepared by thia method contained
tracea of aulfur coanounda which attacked nltrocelluloae
and affected the atabillty of esokeleaa powder. la la
on© of the rsasone why the use of nitroruanidlne in
ewoVsleas nowder did not sops into sarlier use,
j nrooeae Involving the use of eyunaaside -roved
to be wore practical because of the availability of cal-
cium eyraihaitle as a raw material. Cyana-wide itself is
not a auitable raw «it«;rinl because of the difficult lea
in preuarntlon, nuri fixation, and storage. It is a
colorlaea crystalline substance, salting at 40° 0, and is
aolubla in water* etuwr, tleohoi. It yeerizes
rebcily upon evaporation of an anueoua solution to pro-
duos a dlmer, c icyand ia?8lde; on heating or lonr standing
a triaer, KSlaaine, is formed. //^
NH a/v/y
H^-CN ^H^-C-NH-ZN > HN!^ ^«sla?? in« fcM extensive us** in the plastics industry. It
polya«rltes with formaldehyde and urea to fors a reein
usee for adbofiives *n& adding powders.
i ssrli^r method for the coaweroial tion
of ayanaiuide was by treat in* notaaslura o; e with a
halof'en, usually chlorine or bro»lne # to for» ey
hallvls, Dmh trsatlag with, a solution of sjiaeaia in w^ter
ether.
KCN + Xv > A"X -h X-C/V
<£HH5 -r X-C/V > NHH X + NH^CM
k
3\
Iit
VU-"A,\\
\AD-X -v x a <—-
7
If the rcictisn la crrlid out In r solution, the
essRonlus chloride precipitates ind can bo filters off.
flM aVier is evaporate.", spontaneously, leaving the
ey Ida as * syrup which say be crystall I*-*! by stand*
ing over sulfuric as id in a diaiocitor. Cyanaaide ©ay
also X removing hydrogen sulfide fror thio-
urea with raoreuric oxide or removing water fross urea with
thionyl ehloride.
3
Hjsi-c-NH^ * scci^ /v/y,-c/y ^^ -* *"c/
The Low of cyannaide (\h) f roT anleius car-
bide by nitrof»n fixation has wade it mora readily avail-
able for eoiassereial synthesis. *h«n ealelu.e carbide
containing a little o^lciusj flourIda as a catalyst is
brought in contact with fasaour nitrogen at a t^Kparature
of about 1000° C, the following reaction takes place:
Cu.C^ + A/M * CcA/CM t- C + V ?, GOO Co.torie.%
The aalciura carbide is siade froa coke and lisastone
in a soothered arc furnaees
?'
.-
no\,0 008 ,\V> + r
A VV3VO *—4\At
,ojt -^ ,^o^ < Cffc -vfe*^*OS,
8
The carbide Is then crushed and ground to I fine powder.
411 osor-itlone *re carried out in a nitroren atmosphere,
for in contact with relet air, acetylene would be pro-
duced and forr rm fcxplosiivs fixture. The finely rround
carbide le run into an oven with a capacity of about 8000
pounds and covered. The charge ie heated frois th* center
by a carbon resistance rod and the nitr , from liquid
air, la paasod upward throurh the char nco the re-
action exothcrnle. heating ia neeoaeary only durlnr the
first rart of the run. The fora," 1 i on of crude ealelun
eyanaaide recfj ireo not mora than forty hour *? con-
tents of the oven forrcs a col Id block which is lifted out
and cooled. ?h«j orudo prod-.iot contilTe ^*»out sixty pT
cent of calcium eyanaiside, the remainder being quick-
Use, earl id a littin -1 aal tar The
block ia yvulverlred and the oarbi&9 is decomposed by
* t«r. The result in/* da r 1 -colore fixture of oaloiua
eyanaalde, Use, and carbon is known as "llae nitrogen"
cr "kalkstlo^toff *, and is a very ooomon fertiliser.
: oyanaatlde has none of the poisonous action
of nruesie acid and its salts, although It dilates the
blood vessels and thua vastly increases the affect of
eubatanees such as alcohol or caffeine on the aystesu
Besides Use us9 of this compound in agriculture, it has
been used as a source of urea nn& certain cyanides*
I
To produce oyanamide, the caleium ayaoaati* io
-jjed aa%a*« If eatar rvlono is ^-
L« oyf la is product, »• I r*°-
o -or ,-^o-
cryetallina aparinr.ly soluble suhot « of *
8: »* i " co i oaloluo
»alt td i solution of cyanasside all **** of
the in t%«l elds aai Lfuric,
oxrlic, or U. '" onic Mil la the best t t the
Prolyl! is rerction.
solution formed is directly Liable in cer-
tain reaction*, aa for example, the preparation of
various nidlne salts. Ons of the wore resent usee has
been for the prop.-r I Ion of ruan* Iate, which
litloa ae a fertilir. use of the pre-
ocncc o" phor.phorotia nnd nitror^n, l»*i «"•
neoGcc-ry for plr- ; U tl»J '« the
solutio: MttlttS sulfide, th. A eurride of
ft solsc *• reac* I to fort l#-
area. la reaction Is used to ace aeany tons of
lourea for ttta rubber industry. ° r«d
froa the solution toy hydrolysis with sulfuric a in
so
(jrams Of 1)/ cyan ai cun/ao
30 WPer lOOcc Of So/at, on
F/q. H
10
fact, It w%f be r-'e-^red f'ir^ctly frnr ealeiuw ©yn-
a»l*# by utinjr ivlfwrlt *<?1<! an th*» at
-'••
t«fre«
I •yttaaalftt eelutlfl * -ynn-
tl**lA* i* tf*f»«d« l%ii 5* * e^nrenlor.t crcrr^ « r *tr.rt-
lai *cr the preparation 6f gunnl ritr<-*e.
Di#j eryr- LlfM rv*or M•* ^r, h- I<-ble ?»t
etoc I m rt In - tt9 at 0° 6 *\rx? -ta
In 100 M t€ . (Fir. IXJ »? rrvn*ri. t h needles
or r>lfct*g fthieh me
"
cecor^nesc when heated
abor i pelting potr.fc. it ia used diractly in the pre-
' ouc gttanldlne derivative* « Itt reaction
tr theee derivatives f*er>endfl eolelv I the hyd-
rolvels o r the cyan rrouT), rhleh £oee Ml •^
IM pee
>roue hydrolyetrv »nt» to ^ow gv
""-•
.
11
or. I .
-lldln'? ftltrata ifs o p lnt»raat aa an «jr Ive
oslva BlXtuPaa &a*1 as an ir/er-
a»cl -i In tba pra Mon o r nltr- nldln«« 1 ot.har
a<s of Ine r •**> atron** six«*d aalds to lOi*
art then to r -uanl&ine, but tha nl a la con-
Tor by iiaaolvin." it in concentrated in] La aoid
. nourl-i- tho solution into amtei*. nnldlno nitrate
Is a whltr -lid with a aeltl; I I ef ?06°-
it ia a «+.-vi<», Btam-Uyftreaeepla % -'hieaa
->loalvo ea * It la re'i I l aolubl* 1 ol *nd
ary raa&lly >lc in eater reeryat*llir©d
solvent.
;y year* guanltlna i «aa I «-.t»t
e^sny pr k |iia Mat lajajueiily ~ ~lal
- tha af nitreI ina by it nltra-
alda* lnaa f tr
la af -oV<»le«a - >f»i tfea e «»ada
•-*- la li no1 rely anl«
(•ins thloeyaaata la al«' ; Iffla ri-
'•, m ^leasnnt to "«.«•
v
, *mar
an<5 Ball y is mal r sort-
ed Ido h<?at«d with air ta
>e thiocyanate In a mm 1 ylald. Thia
'
urotation takca plnce baa&uaa the ntf-mo). v«ite
Lly fuelbla. is f .•, iggestftd to ?)
t another a^aonlue nitrate, which la **.lso roeJlly
>!•, o thro*. " lit «&ee tyv>0 of r* ,.
i-i.. oat thooretloal yl ie
-•"-.f Ui
»«thoc: mm d«« u»©4 for the Mon of
.* ©*t itKV$1 ,--. tWO
koI-s; mi* ©f nltr . ri«, in hit
rir»t experiments, used a ( tub© he t . oil b-nth
© £&»s first fusM, celtec?, then beoasse
soli te nitrate*
oil b th or fso -•« equivalent method of tattling should
be usc<J, :'or if :><? crlxtur* of th© two so I
Im tifor •, 3ecoispoaltion wit! I i:m of
atteenla occurs.
M pi 3DS. in fell* first
'at- :! nitrate raac'c with I ©up of
to for ilde nitrat , is the
of tho r ". ,. . .le
ate th«n re I &nl * . b to give crystal-
line p>v»an3 Itr&te* elcoul .itrate
:br *vory »olecula »£•«AW Nti MH
u, v\v> \wv
If . - the &i lia«ids i- r**#tlon
^ea n lssnr^s a at.
.
ur« of
nitr
i
'
. la
.ium nit la th<> f the
K>". jrt " '.oaa the e >, ll it \cld.
r • lanitle •, If ttftl
ttltr its
formation supplies tuireleilt of nitric
.ere iri, tharsfore, I llM earl rt of the rs-
lere tv.s? bi--w-:ide Nanonltrs I ^.ek
the sjMRonltni r.lfc
.1 iber 4
In Y ssflsenlmi *»r thlB reason
the pro#€4 lv«*» - %«sa of
astwonluw altr is utsd.
ibett*, sad Heiabaea (16*J st the same
• for the 'on if nldine nil sing
)8 fiT-nr,:. , rsaiilti"- 9 to
found
»nt in If half
1 the toftonli ? is fused * I
:i.; the
Lxtur *e
in . y , s reaet '* s»
ore > rooess
''or fche sanuft re of idine nit:'
~e-
Of arlr. ' . !. a of
uabb I nitrite V if rtI . found
-.ot interfere »11 : ... the
pr 1 ..•. u98 the yleic &rejRti -
.Ine nitrate K?ay either be rscryntal-
or thoroughly driet erode ot&te.
Lf (4), I eaall b .t of m nitrate
preeent dees not int^- it© eon-
vc _ :anldin s presence of tion by-
ire. ith, ^at>ett.,, ..-;baoh
( 16 ) f sjore than
ine tiitr ; the remainder
excess aianoftluis aiirmt ertec ejioyan-
worphous '
i 1«
ifaoture of explosives, ity la aa ia-
pc ~. urity of i^niclne is
.i the purity of the (& aidini ni-
trate u- ration, it is n#eeaa»ry vp a
neth i preparation filtrate.
iaence of soli he *••.«&. a te, o
16© to for» r!x>n di-
oxlde, ; . no an-
. . • Del14 •
. . ine
r» »el-' , »o
\ereforo,
the tares coamoundo* arctnelide, Aaoelir \<\ Tselarine are
15.
aaonr the ;?oaaible by-producta found In the ao-called
"ftijorr>houaw m I .
"'her 3 "aajor^hous'* material I in con-
oe I 8ulfuric Mid bo solution i* poorM into
cold w*»ter, it recryatalll~ea. oroforOi In the nre-
: o r nitro -uridine fro- th* crude "h^nlon product,
the *ojk aot" .Tateriil reoryatallixca *ro «u?lfvirie
sold tlOaaj with the nitre ildln*. The reault nro-
duet reseablee plaaa wool instond of tho finely oryatal-
line forw c | ^ed wnor. DOTO ?njmnldlne nitrate is used.
The ?r-3B taoo of theee 1 ^itleo nffeote the ehovlcel
properties o* nltro-uanidine. >"or eya»rle f they de-
crease the eaa© of reduction.
iy lo*»hl&n lor*a quantItlot of crude pruanldine
nitrate with T°.tsr a ??urit? of °°.l oer cent enn he ob-
tained, ith, bto, (if) eoonnrod tho
solubility of pnjDnidino oltroto and the "arornhcua" wat-
in water, athenol » ?5nt* oothanol at rarlooe e^r—
•mturea srlth tho follorin^ roaulto*
'olygrtt.
or
LOftOl
ol'
•ethnnol
nici'Units »ornhmio_"
, Atrial. .QS?K.. gAOfiti UtfU. ~/109m
39. 0.1575 '.", "0 1.20
'».! 0.307^ 15.
.7• 0.10
$.6
., ' .
-
MfJ
ceM /\mwf tiai* /* fattriA T$&r two 'ifek.vfu T/oit
lf-0 iso 1 60 IK) (90 I to 300
T, teiriperature
Fig. m°c
16
Therefore It can bo wmm k
ould
be used for the leaehlnr with f*oort ~« u.tt».
The yield of sj ti nlt**te end the -
rphcus" snteri^l fwmni is * funeti~- ef |
erraure and the tttrmtlc f the f | v round that
the beet results could be obtained if ture was
*•** ti | the duration or the f «,hout
I hour. ith, labette, -roved that
this was true hy conduct!i us] lees ef
one and two hours for the fusion, «t virl- tort*.
r one-hour fusion i they got ^p
sent yield of gtmitlsUac nitrite with cwt
"ascorohou aHMaterial* . 111).
illy pure (fWiiAlftt nitrate nay be obt '-.ed
by uol 9% witer, tV y aeldle with nItrie uU,for irat reeryetalltsatlc fell prodvet is the
M '«£ in sola water nasi erauorI
' » ori-
ginal voluae *nd crystallized. third reorv Uonfroa methanol yiel-e our- ttlAiasj nitrate.
nidine nitrate] U I ~raetlr- nw »- ;n the
oroductloa of nitron ~ md other mini^lne rterlw
tives becnuae it i» easily nreoirer I easily converted.
It is also non-del loueec easi
J.
.
17
In 1 biele T^re^TtA altretailid in* fr©i ri-
te 1CM ltrate by tr >nt Of
•iter » "le * In fiteinr sulfuric a Xn
SMS and ¥o (10) eon-fueteo eTParitrenta on the rre-
ion cf nitre i^inc frora aruanidinc nitrate* They
eonolx'tie^ that the f> n of £2 + ^ " ->er cent sulfuric
acie on the selt 'or *
f
; hours before Tilth »<%ter
yea the best yields, eae investigators used one
cubic eerr tor of the acit? r>«r rrp- rf , . Jvis
sine*5 be«n found, that if two cubic cent ii?etera of the
acic ia used to ev*ry gttup of the s*lt, the tire of the
conversion e*m be cut to minutes.
oeess in the forration of ftltra^uanldina. from
*uanldine nitrate by action of sulfuric a< en
•allad a dehydration oroceea; notually it ia a nitration
ooess. Xt his been shown by uavis an -field (7)
a acid i\ the id in* nitrnte salt ir ttftt at-
tr\r:< ttm nr an ».*
'
ie at-
tached %t in* molecule na a whole. 1-
tion of the concentre f j aria ^3 lb, w '^e
dratr Tp-ent, merely causes altn 1 of %h« amine
«rrr>c;r< to take olaoe./Y# NH
Xn the oonvereion of quanldine nitrate, it haa been
.,,.-'
i
;
•
v^i.^W
L*VW«>\*- o-nk^w
irneiIn Hours
tOf Oe hyc/fo^l i on
Fi9 . n
foun *r yioitie of tlie (k*d If
nit; ?'lod is less than our. ('.. con-
dltioa* accessary for ^.hla are thr-.t tv.rate
finely c;roi. wparature >•• regulate . Lth,
•aat ^n
alrture bo - or v., i'oves aaA
Carter ( I ound I^0 t^ cwad
to rlM 3 -•'ithou'' 1 . . If a
Ion aaw , o Bulfuric toads
to ;ly7^ iidine. jam yields fire ob-
Insd trhon tlM nitration period in 11 I on - If
to one hour. I . I $ a&xiaua yiel raised
by uainp, aore than t 1 rainiaun of *ici. . la offers
MM e in the rol of re
is aade easlais
exists in two distinct faraw . Fa*
alpha form 1 nnidlne nltr- I I solved
in c r,no'?r; f irli tr.e solut ured
into w ter. It oryr izss froa water I , thin,
•t lustra 1 . «hlch e
olr. . ,de«
s tfflejult to pul . ta fora
with spae v tti 9 f is a: e
of the alxture tf guaaldins itaaon-
e which ratalta fraa thl nj /sis o r yandi-
aalde with sulfuric acid. It crystallines froa water In
m*
If
for -lifct tluatrrs of wmalli thin ©lor tei.
! £h 6 3
;
-leu fr the
Itro ii-
,ion 1 ve all •
.«i» of
>portlet b*1*»
c.
. bo e tlon
a eonrenlrn*
Ion of tho two froeti<
*r- tly In
o solubility our lo olo ^r-
ont .*OBfl lubll-
lty I- . , - \
are It. 1e . I P# t«t-
v b*» the t• le. (A)(5)
Lrte«' ited
•10
-' m
r. take*
U jrloldla «•
- two fornt *.V:e In derivative formation
30
•X*'
'
Bftltl , \ ut
A//V
fIra' •? of . ?.u*
Is WT&r&d, !« rv- m«
I ti nltrei 'Irrst 11-
rtii ©f f|
\d*) 1p
If %h« 0Oj id fo
nit, 7»o *•«
.14.,,.
16
V\\A
,3V\ttV\- 0-V\\\
&r Xy on© auVffi *•
". yltic
»©*e e«» have er! In,
&t» of 1 ^y
i i-
is e-'
•. a-
id
re
-o of e: low. 8 so* *>•
' 7° C
.
rretav»r«« ex»rt,©3 "by th©
0-10
Ve*<sc£y Or L
Fis-Y
20 3D
Concentration Of Su/fur/'c Ac/
J
W £0
f'S- '3L
alii tt,
tt CT I > V),
Ltvtc i t tila cftict lotion taw-
» w&a too 1< • •, jrftror s . L id
isat oorr^c*. Mm «?-
9 to »1"
, very IIttit It f ' -
Lot •
mt i^ nott ec -saad
. . i». '
'
-»
rlc aotd It uttd* o£uani-
\f ln.Bod©r»t*ly ooncar- 4 told
I), r . t«d If
iota of
waters
;t 8*5' it that
to ii 'ft Xo mad
owdti •->*«•
der tul for iis«, tl »1 may ad
Afgal: ^.ovodt
or
23
t'narp.l, 1 nltrorx inaa *ra oolorlaaa
erystallin* aoilda a r "»ataly aoluble in s 1, in-
>la or n " fc-1 y nolublo In oold * I o soluble
->r « Hy aoluble La othar.
v? ir la* *ra alwllnr *^ &ho#a nit.n ;ldlrta«
" the nlkyl-nitr involvaa
<we«n o nidlna and tha b : ^riata
1 orl^.lnataa froa tiia ^ent
of a> asnidino. Aa aho*n be a-
r«r cyananlda »rv r to
*» quaouf aolii-
.nidino ie> >at«d alt) M<t a assail
n ; jie, a a of
- 'nidlna
aa i y -uanidin© la fer»ad tha
ha amine oi pro*" roa the
firat P danpranra«ar a -alkyl^aubati*' *' id nraa
la ' Atro *,dln« ro
er hydrolyi •'hJ.eh
a naina. -•. lt.ro. ia fora-
' m ^r- t'u: filtraayanai I i ^^o-
• aeoond aoda of S9hr a: anNH
HNCAj-No^-t tfNH, * RNH -C-NH-NO
rocaaa, o 1 *ly msr- ... ^
r. 1 r lne 1 • 10 pa a solvit i^n
af * -I Ln«. ajlxl y* a
nltr K>lil
• ••
is 4 —
•
1 8 f?"
alc^je la
:.--
1
f
;
I la
<39 (8)
on vrioi'E all ' ie» • 'methyl
MRlne is only a*con<3n,ry as laa *hlcn r•••-
"**• e aero riroroua I laant tfc + ha
'laiary b* wore concent
r
tlon df %1 - i«
is rcuiired, "lao r te o,
t nit v nl£ine 'ie
' -nit" it
fll-11 nit- . (7)NH
UNH- Q.-Nt4NO^ *=^ &NH-CN+- NH^No^
The ac.cor.Z mod a ' It la ^eparad froa
nitre lna« a renctio 1 Lna
•*
p^:3^h + ,^^ >W*3-*ua<h
a
tolvti ft d* e 08 It* ; ^e to
broui oxl-' t"m» first ' lo*-
. . I one
•
,
ildlncfta la Itn
»r a prl •..'_fcyi
i
ta U ir 9&i«i
r***nt "
Li ef
9.
...... -
,9
pn iadur* aft J+ h« prop: r-tion of ni i-
?hs I 't of
nV is - It,
In "uric Bold - Lnto so '- bat** *a r.re
•of - , rtavarar; nitration noon not t
to »
-o .
26
of
' ',fi;;hono >
HiN-C-NHNH-W-AhC-NH-NH-AlQ + dH^O
•th «r » «ftf »n tetr. alty ln
m' a dene It
j
I ic M It.
** It .4.
•.#* r tin pari ;.»
tMtl of ellYur 9. <m«,
h »»1 ry, i« utible at o . ry t«aoa> m, but
d«oo*po»ofl «b«n boil#Kl with water, to «voivo I ,«i
v>*V\
V\';
aw . v\
WW
^ VvW jW<H » OV\b H s
+ :p-\^VV\^
V\Vs
O^i. + o\N H \A -W* - j -V^W-HWVW - \j - V\ ,W
&frj>r&j$si&*f<r
8ooc
^B
Sand Crus/iGc/ In Sand Test
Fia. EZZ
17
°''I »1« of t«jtrfcc .*t 9&
'
I• -
9.
f< '"' * St
lfh#n u ^ v^* •
Ul ' a vac. xt is
It
ill . >e •] - -. C©1.
uflf • a« an
•Bly 1 Lt ii rt«n lait
it» ••nsltlv:
—•
i
asi done by Phllllw* anfl *13 j) -t
I of ffalo. orfci r * J in«
I TV? i ii .
'. of
lnad a yiel of
d fo) tionr. •&:
HN-C . + *V//j
\
TV///,
lite cryat "111 :.e
".0
:ts.
It rr>elt.-fl ' Wit' .d
-;<*to toa« ' he v
I exr- La •-. i •,'.' a
--
-
is. | a is •
e r
:
y\w\A *VA
,VM ->A> ¥ ^NAVWA j-Y^
<i& + VvV\«r <a >* -v AWK V* D * \A VAtWW * WH
*x fc + ^ c^Vi y>\ r 3-NAtt
-3 =
he
. . I ro '.to. o—
I no-
•tonat©
! the
-
*
! ) r©-
I
. ..-- nd
ayl
Q AW +c^VAVWA
j,^0~WVvVv /
~\AVN
- *N*
U no*. T»«d 7**
I 0*.
- * of 1.50, is '( P
a In r~pl»i .
•
th
Ive te h«it i
i .
-
—
^fliftft • 4 by
a or nlt.r Ua l9
Lu« 1*riftt
-i
I lt*r-
0r"
'
;ani-
tioal
, frii , . *«• in
r ' Lc: 1
® •
I
;
i .,a.
. one,
. - .
10
(1 , . . .
%Xf , . *})«
(15) rrv9 end Carter, Xnc!. nc Ch«*., "*6, *32 (104A).
»-
•r f T • *
,
DATB DUB
.ssis
ft 66 ihlinski
7862
AUTHOR
Guanidine and its nitrogenTITLE
1
derivatives
— ......
ive;
ACCOPRESS BINDERBF 42056
MADE BY
Acco Products. Inc.LONG ISLAND CITY. N. Y.. U. S. A.
thesW66
Guanidine and its nitrogen derivatives.
3 2768 001 90005 3DUDLEY KNOX LIBRARY