NITRATION OF SATURATED HYDROCARBONS AND THEIR DERIVATIVES

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP82-00039R000200020070-1
• Release Decision: RIPPUB
• Original Classification: R
• Document Page Count: 12
• Document Creation Date: December 22, 2016
• Document Release Date: May 15, 2012
• Sequence Number: 70
• Publication Date: May 21, 1952
• Content Type: REPORT

Declassified in Part - Sanitized Copy Approved for Release 2012/05/15 : CIA-RDP82-00039R000200020070-1
NITRATION OF SATURATED HYDROCARBQn1S AND THEIR DERIVATIVES
NITRATION
Ghur Ubshchoy Khimii, Vol 18, No 3, 198,
Source.
pp L73-.L78
Declassified in Part - Sanitized Coy Approved for Release 2012/05/15 : CIA-RDP82-00039R000200020070-1
STAT`
 Declassified in Part - Sanitized Copy Approved for Release 2012/05/15 : CIA-RDP82-00039R000200020070-1
IT I'rRATIO OF TOLULT~1 INTO PE,1}aYL-~ NI TO-TE'JEaJE
A. I r Tjtov, Laboratary of
Organic Cherais tr'y of the 1ilitary
Acadonty imeni E. Varosllilb, 0 ' E
The pruson f ? work re1.~~resont.; tho practical application of our t}leoI'y
t
and she aiky1-be111Ze11O side chain for the purpose of
for r!itra~inparo.ff~.ns
evelopl.n,~M hod.s for obtaifa.n , mano nitz'o derivatives .
d, T ne ,
. nl lrrlov~n way of na.~l;t'atin~ toluono and other alkyl-
Till recently the o y
the cl`i.ssica1 method of I. K0ova10v. T"ne lab-
benzene uid.o ChL1],T1S has been
i-
~',thanc~ by ]aeatina mixture; of 1iydroca1b0n and ia.
tee' obtained phenyl..n~.tro rr~ ~
~. gravity 1.12 in a sealed t1.T1a e over a waterbath for 4~~
tric acrd a,c si~CCa..E.~c ,, y
hours .
ted Konovalav from describM
s preven
.., an mechanism ha The 017SCL11 C, 1 CaCi ,~ ~.~ ; ^~ ~ ~ ~~?; ~~'S.
,1?y r:~.p,t r.", r.y,~. W ~ +:. +`?...., ~ ,.~ t,~ ~.. ~' ~ , s ,'tr~' b" C~ per-
, esis a.d?egua.~~eJ.i Thus, tho i onovalav ecx imnen '5r1~:
:i,n~ tn.e s ~h ' ,
? M
'i anal C~;ollcrian? and Van Raaltc, who either did not o o-
f'orri>.ed in.dependentl,y
- ~ '; all or at r~.ast obtained 1.~2 drops of ite ?'~1oi'I~har
'vain phenyl-nitx"o-rna~,hane aL a
alav des ,ite the
f w ~,
could P. P? Shary{;in (1.) r.o,~ica:?ta. the results obtained
?~al.e than. the data of the others. Slr.oryg~.ra' s
face that his data were more :~avard.
l
f
.
u
r the reasons of the failure v~ere not SUCCess
attempts to accaL~nG fo
C n research in nitrating toluene in the side ohain, we
,
(,o1m. ~inua.nour
4
e. ~& M sx~adan~ the ~caction ir1 open con-
nalnr satisfactory methods for L
fl OW
So a h.L~T1 ~ dr~c~ds of n'ram~~c; of pl~enyl-rm.a.tro_mathane. a ni-
u a. ~0 obtain '
r~lL, r, pBCi~'iC
agent, nitroen .~..~a..~d~ can be used a, well as ni~t,z'ic acid ~
tin
~;
tra
Cniadfor a period e~' 4 hcu~':~~?
to bh hoatecl. at, X10 - lOQ dcgr0cs r
ravty 1
h have been ac1'iiev~-
'
rr
t
from the data of previous,The~;c~ rc,sults, verb different fran
0 r.s Fs
d 1 ,,t}pie foli.oWin~ bheor'e?~ical analysis.
C
t re orts (2,3)) the 1nechanism of forming mononitro
`~.ccordinto our x~,r.s p
r derivatives with nitrogen oxides. and
comauncls by nitrating paraffins and tliel
p
Declassified in Part - Sanitized Cop Approved for Release 2012/05/15 : CIA-RDP82-00039R000200020070-1
TTRAT1l) E DR0C~JRl'01:TS MD TI:JJEIR DERIVLT1\~1aS
~l. J .i'J. S~,'1' ?M.?..w......
`i _ r _~ __ OF _........,:., __ .._ .,_._..-___,?,.....w,....,.....,.w.?.... . ,,,.w
;~rC~1'~T:l''.1;'~~~a '~~h~CVA.J.
I ~f
~z t~:[:~.,rl;l.O1~T C~~' ,(',
I1 . G r 1;t0l ~+~
~,~T.hS~ T~1~u;1~,~,
STAT
 II
Declassified in Part - Sanitized Copy Approved for Release 2012/05/15 : CIA-RDP82-00039R000200020070-1
fli'lri(: oid. is us fo11ours ;
k ,
~~~~ ~ ~" ?rf4 G~ `~ ,. rf "'^ " ~`~ , a) h"dx' QCC1rbQ1,~ wa.t).x mono
mer ic; nitro ara dioxide:
iZu +. NO a R 4 E[1~TC)2
6 a 'v G .
1? subsc uently, alkyl ib: s v1ih the radical m.oieCUi0
RH&. ;NU2 ~ RN02
The most i:ciport';r,nt ieaction competifg w1'1ah the laber process
,
will be the r~ 6 or' aikyl with n iro6fl oxide a rhi$ y
is cor7vor`ted in'co p~renyl-~dinitro~
10W~.i~.r, n,~.1;ro-corTlpol;!rrCt Zti`h:l.ch sLl}oscquen'~~l.;r .!.~ .,
? : ,; ` v
~~' V;ror'c~al,3(7 Clearrca
methane as was shown in the provioias report (u
nd,i'iorrs for ni-broco-cornPour'ads a.r.ito raorio~na.tr.o doriv.~
up the corLvGrsion eo
and other produc ~s a '~f
tisres
A Su]aplG~lEn y accessory roCLion appears to be the interaction
of `-ho radical with dimeric ni ~rogen dioXi de N2 O. , givifl
~
ducts which will e explained ir'i detail iii anothe::c?raptr e
oX1d.ized pr a-
From 'rhe ?'oregoin it follows, that for acceleratinc the nitration
of nitric oxide in the liquid p Lase anal guid.ing it into the a.irec:tion of
f :ni n~, mono~nitr'o deriv'ati'ves, we shonJ.d build up duri.n, the reaction
z su~..Excie t; cuantity of a`iD; and, roduce as far as possi'b1o the cor Ceftr`aGican
,~
of ~.J ,y1.2 C) i , ~)'1(()r'kin , with. open containers we succeeded in perforrnif
NO and. .
the reaction at a temperature of a'boUt 100 degrees and. by employiIti ; an eX-
c solvent or still better the hydrocarbor1 itsolfo The utilization.
osy,, of
of a large quantity of hydrocarbon guarantees sul'?'icien'l, conce1~tfabi0n of
fro the reaction, and the tonperature rise is of minor importance
~~ dltr~.n~; the in rc1ar t_uion t0 1J0/N02 NZ ` O. /N02 due to the sharp decrease in the solu-
and she cofsid.0ra1D1e increase in the aissociatio~rr
bility of nitric oxide l
of 2 0,'1 Whlctr approaches 100 percent, under these c"onaitiOns I The de-
ffoct of 'be1nperatlzre and the quantity of hyd.rocar'bon on
duc'L:r.orr about the o
t:h.c yield of the, mono-..n.!. ' tro derivative has been fully proved by experiments.
Declassified in Part - Sanitized Copy Approved for Release 2012/05/15 : CIA-RDP82-00039R000200020070-1
 Declassified in Part-Sanitized Copy Approved for Release 2012/05/15 : CIA-RDP82-00039R000200020070-1
Ipara.llol with tc~ i1s,o of excossiyc1'ocar'bon, a 0d h1 inM
cr'car.sa in the yield of riono~rritX'o compounds has also IJoen hra~a;ht about
introduction 01 U"~ ~"f7f dur' n , the ro ~cti()rr a This iSu explairlad introduction J-~.Ly
CGf~a1dr'bons ? As it is shovrn by the stoichionlctri.c oquations
,('o11cavea.n~
of i'aa na.ur ,.a'La.rr and oxidiuin reactions With nro;en clioxido, as follows
2G H 5CFL -- 3\')2
2C
J:f. . Oh';) i'T())
H 20 NO
C6 H CH + 3No2 , Cia (JQ()ii 112 0 + 3'N0
All of them form nf:E'ic oxide by the unpz'oductive consumption of nitrogen
dioxide . ,lfcirc,.rtlstafce i.rtvoiVGS ~l red1.1ced partial pressure u.l,1d con-
a. C~)fCefY'Lof of1,iO7 in the h'jrdrocarlJon, 'Vdlalch decreases the
sec{uently
rapidity of the .. the act'iono The introtictiorl of oxy'r'-;en, i1ianSformin rapidity flx 1'''G the
' ' _ into dioxide, ough. ; to cOrltr'1OU ~e to the more e r'bens lve and
r.11~GY 1C 0~v~1(.lG
a_ a-...e y d n f;r'ogeri arid bo the acceleration of the reaction
cGrmpcomplete use of the r~GUn
'
r'a'te , a fact CG:7I1.r'I11ed b ~1.o OY.1C1.1Zlnunder these CGi1d.lf~a,oTlS
by eY} erl'n?~: Jti T
- he final analysis took place eXClusiVely the expense of tie ox;y onr
For cff'ective nitration of
toluene side-chains by nitric acid, ac"
cordirlto our theory, the following should be provided:
1
7v L)'rT r. i.) > >'ii~ r '~ i ~7~'(~~?~~j~ ~,~~, L)~~
( l ) iIT' I. :L r:OG.Ea ,.... , (.1 RAC ~..! r4TI ~4h
S F.ES.u~. AT
,.
2 rr`I [i l'1,L P O[~ ~iTI TRI (.~ Ad. ID 3TJi L1) U? 'JD aJ~ T.fE
ti:J (JJlj ))cJ:L J.
REAC TI ON
1L)
CO . Cr TRi TIo:i OF N 0 . ll iJI ?~i1.} 1)~rl~ l ~~,YC~ '~'~:I'i i'VJJ~IJ
',1 !;;.i .~T i ~;) .I. ?~ ~.,1~ s _
y i 1 i CO1L j 1 ,i, s TO ;,;JI' '7a-J: ~ry .C~1:: i i~'l:Z.c'):?;) ~w11 ;:fi 'J::(l~j 1~L
`~
. TO THi-a NIJ VLEUS t'1) FR.UI T):r~ 'i'ROYT2' G THE F(,}~ 4lil?G i'I%Ei `f..~
QBSElt\l. , CLE OF T.!i.L RLAG t r" T1ICK J)EvEL~ ~l%'~~Cp.FOR ' THE I ~~,1Fi,1`w`i ~'~E~f
'ta:~a~a C ,~~
l?i TUI LL `fi~()G'Etd~ iDIOXl: 'E
To e first conitiora it is sufficient; to add initially a
f u l f:r.17 ,.th
certain quantity of n itrogeri dioxide or substances which can produce the
Declassified in Part - Sanitized Copy Approved for Release 2012/05/15 : CIA-RDP82-00039R000200020070-1
 Declassified in Part - Sanitized Copy Approved for Release 2012/05/15 : CIA-RDP82-00039R000200020070-1
l'l1X'i0 ~1.C',7.C~, such tea
p y 'a c'b J. n i:a VJ 1 la ~1
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'
t s
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of `I;~10 paX
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:fr?bh()x conf:>rrB~oc~ by `bho cxpOx';1.r++.ex
,bx'u ~..x ,,o~~ar' r)cax,oa,n,d acid a~k; spaaa.f`~.c-
,.~
~ n~.'G2'a~~a.on of ~oluone ti?~~. ulz na.k,~, }
lLti1, of raox'e ?l,~.an 50 pe}~cc~~'L 'l.}?xo,n s'Loa.chlo-
.~ , -~,;~ ar.+ open ve;,7clu ?M an o~~`~a
~., x' I;~.v~, y
reo ?l x':LGaf tr pc, S s i to.i e , UYa 5 a'~ GC;.7. ~?.e d 1
, ,, s c~1do wac~ c~,s
~ the accc~lei'oa of ~"~.r~ 001 ucx s:>.an o~ ~
~.. method. for
~,h a a l~.caw
,
r by -L1ie a.d.di-?n of mines as px opoSe(i axd te
x~~ and SOCO'('!C~aT'~!' x1lanOx~:L'a GOr(1pO'1~x1C~u, tiVc~.u
~~lln?~ ,~
Thor' the Gx~;~;'acLa,on of px
eatcished.
ri I,,...i. ..r.., f
R4.a',J LC. ~.tK
V Z',,I~-~~.El~l), 62, 675 (93))
, P. Silory~~.n and ~okolo 9
1
21 1 jtov, ZU-0i 1h, 1B96 (196)1
a~ 1
V /
da 1
`Cj'cov, Z L-0-Kli, 16, 465 (19B)
P, ` , tov Zh.-0-KU, 10, 1(Jr(i3 (1700)
L.I_ D J.'d. 1 .~ ~ ,
i orlova1Ov, Z. {'()iH-O, ~1, 25< iB ;
"j .e J.l~
.C 1 4 9
c) ,
Suljrai.~led o EdfOria1 0f1'i.Cc
FebrU ';)l Ca 1945
Declassified in Part - Sanitized Copy Approved for Release 2012/05/15 : CIA-RDP82-00039R000200020070-1
11