SCIENTIFIC ABSTRACT YAKUBOVICH, A. YA. - YAKUBOVICH, A. YA.

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• Collection: Scientific Abstracts
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• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

4'.
7r,,-2-6164
AUTHORS: Yakubovich, A. Ya., Pravova, Ye. P., Docos 1073"Jiy' 11'. A.
T IT LE Syntheses of Vinylvonomers. 2. Some Derivatives of 01--Chloroacryl-
ic Acid(~intezY. vinilovykh monomerov. 2. Ilekotoryic proizvodnyye
ot -khlorakrilovoy kisloty)
FERIODICAL: Zhurnal Obshcbey Khimii, 1958, Vol. 28, IIr 2, pp. 320 - 321 (IJSSR)
ABSTRACT: From the acid halides of o(-chloroacrylic acid the authors pro-
duced the fluoride of this acid which was hitherto not described.
The synthesis with a yield of 45 % vias performed accw din- to the
method of A. 11. Nesmeyanov and E. Kan (reference 1). The attempts
to 3ynthesize the acid fluoride by heatin,3 (160-1700C) of oC-chloro-
acrylic acid with benzoyl fluoride or by the exchanre reaction of
the chloride of cliloroacrylic acid with potassiun fluoride yielded
no Positive results. The acid chloride3 of o4-chloroacrylic acid
r
was not obtdned b, dchydrochlorination of the acid diloride of di-
chloropropinic acid (refere,-ce 2) but directly from oC-chloro-
acx"jlic acid. The best yi(X- (4QA~ was obtaineJ by the action of
benzoyl chloride upon the acid. Wien other acid chloridei (PC1
SOC12 C6H Ccl ) were used, the yield of a -chloroacrylyl Nlor-
ide wa's smaller. By means of chlorine- CC -nhloroacrylyl it was pos-
Card 112 sible to synthesize p-cyclohexaphenyle the z, and If-phenylaciide (hith-

7 ('- 2 - 6/6 ) 4
Syntheses of Viny1mononers. 2. Some Derivatives of ce-Chloroacrylic ~.C-Jd
erto not described) as well as the ethyl ether of od-chloroacrylic
acid in the usual manner. Accordin,-j to its pro,~erti2s ethylc4-chlo-
roacrylate did not differ from t:ie ether which earlier described
(references 2-4) and which was produced by the authors bj -.loans of
etherification of a -chloroacrylic acids with ethanol. The above-
-mentioned OC-chloroacryl derivatives can -ive polymers and co-
polymers with vinylnonomers. There are 5 refererms, 1 of which is
Slavic.
SUBMITTEDs April 25, 1957
AVAILABLEs Library of Congresu
Card 2/2

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MOTSAREV, G.V.: TAKUBOVICH, A.Ta.
-'I
I - M-K-Aw-
Halogenation of aromatic 911anes. Part 3. Preparation and
proportion of cblorine and bromine derivatives of benzy1trichlorosilane.
Zhur.ob.khlm. 26 no.9:2622-263o 8 '56. (KLRA 9:11)
(Silane)

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ilea by fortnation
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AUTHORS: Yakubovich, A. Ya., Razumovskiy, V. Y-, 79-28-3-25/61
TITLE: The Synthesis of Vinyl Monomers (Sintezy vinilovykh
monomerov).
III. Note on the Synthesis of Compounds With a Carbonyl
Group (III, Zamechaniye k sintezu soyedineniy a
karbonillnoy gruppoy)
PERIODICAL: Zhurnal Ob5hchey Khimii7 1958, Vol. 26, Nr 3, pp. 660-682
(USSR)
ABSTRACT: There are hints that in certain cases an easy course of the
11annichs reaction depends on the nature of the used base.
Thus Levy and Ki "bet (ref. 1) noted that 2-acetylfurfuran and
formaldehyde enter latc~eaetions with oalta of dimethylamine
and dipropylamine but never with a ea: *t of diethylamine.
1:annich and Heilner (ref. 2) described the synthesis of the
phenylvinylketone when using the hydrochloride of dimethyl-
amine. Joung and Roberts obtained the same ketone with the
hydrochlorine of diethylamine. The authors synthetized the
Card 1/3 phenylvinylketone with the same salts; they found however,

The Synthesis of Vinyl MonomerB~ 79-28.3-25/61
III. Note on the Synthesis of Compounds With a Carbonyl Group
that the reaction with the hydrochlorine of diethylamine
takes place considerably slower and that the yield of the
hydroahlorine of dialkylaminopropriopl~enon is smaller
than with the use of the hydrochlorine of dimothylamino
(63 to 75,5 ~ correspondingly). Phonylioopropyleneketone
was synthetized from the hydrochlorine of dimethylamino-
methylpropriophenon. It turned out that propriophenon and
paraformaldehydo do not react with the hydrochlorine of
diethylamine. A.,-cording to Ynnnich also the 2,5-dichloro-
phanylketone was synthetized anew. The 2.,.5-dichloroacetophenm
and its paraform react only little with the hydrochlorine of
diethylamine;easier, however, with that of dimethylamine.
The ketone obtained here easily polymerizes in the
distillation, even in vacuo and in the presence of an
inhibitor. In publications referring to the most simple
unsaturated aldehydes, the acroleine and methacroleine.,
only patent data are known on the synthesis of the oximes
of these aldehydes. The authors synthetized in a new way
the oxime of macroleine by reaction of the meta-macroleine
Card 2/3 with hydroxylamine (yield 65 %)-

..The Synthesis of Vinyl Monomers. 79-28 -3-25/61
III. Note on the Synthesis of Compounds With a Carb3nyl Group.
There are 12 references, 4 of which are Soviet
SUBMITTED: January 249 1957
Card 3/3

AUTHORSs Ginsburg, V. A, Yak,).bo-i1r:h. A. Yao '79-28 3-38/6"
TITLEs The Synthesis of the Element Organi-, Compounds of the
Aliphatic. Serilea According to the Diazo Method ( Sintez
elementoorganicheakikh soyedinenly alifaticheakogo ryada
diazometodom). VIII, The Synthesis of the Element Orga-
nic Compounds of the Vth Group. Pho"phorus Organic Compounds.
Experiments for the Synthesis of Di- and Tribalide Alkyl-
phosphines and Some Reactions of tho Alkylshloride Deriva-
tives of Phosphorus (VIII,. Sintez soyedineniy elementoy V
gruppy, Fosfor_organicheskiye soyed'-neniya. Opyty sinteza
di- i trigaloidalkilfosfinov i nekotoryye prevrash,7heniya
khloralki!7nykh proiz7odnykh foafora)
PERIODICAL; Zhurnal Obahchey Khimii, 1958, Val. 28, Nr 3~
Pp. 728-735 (USSR)
In, experiments by which the authors tried to extend their
own discovered diazQqynthesis of phow9phorus organic com-
pounds of the aliphatia series alsQ to the 3ynthesls of
secondary and tertiary alkylphosph:1nes, according to the
Card 1/5, given sehc-me 1. they found that the ~hloromethyldichloro-

The Synthesis of the Element Organiz Compounds 79-28 3-38/61
of the Aliphatic Series Ac2ording to the Diazo
Method. VIII. The Synthesis of the Element Organic
Compounds of the Vth Group. Phosphcrus Organic Com-
pounds. Experiments for the Synthesis ofD1, and Tri-
halide Alkylphosphines ani Some Reactions of the
Alkylchloride Derivatives of Phosphoruq
phosphine and a.-chlore46,,hyl.di(,,hlorephosphinr, react with
diazomethans but that., on the conditiona considered here,
the di- au.4 tri(alkylshloride)--phosphines were laoking.
In their plac;e phoapherlAs organim compounds of complisa-
ted structure were, obtained which,, as regards their pro-
perties, were similaz to the solid by--products fcrming
in the reaction of the aliphatic diaz~compounds with
trichloro- ani triphoephorui bromide.. In thq ^Ihlorinatiom
of the product obtalned in the mentixnea reaction tri
(tr4~.chloromethyl)~-pbosphi.ri.ed4-chloride., di-(chloromethyl)-
phoephinie- and phosphoxii~. acid were i3eparated in form
of aniline salte. Investigarions arf, .,arried out with
regard to ths reaction scheme and the structure of the
mentioned compoundj3. It waLA shown that the chloromethyl-
and (1,--chlorethylphcephinates at, bigher temperature enter
the reaction azoording to Arbuzov, the eaters of methyl2ne-
Card 2/3 and ethyl enedipheaphinic acid being f~)rmed co-rrespondingly

The Synthesis of the Element Organic Compounds of the 79-28-3-38/61
Aliphatic Series According to the Diazo Method. VIII.
The Synthesis of the Element Organic Compounds of the
Yth Group. Phosphorus Organic Coompounds. Experiments
for the Synthesis of Di- and Trihalide Alkylphosphines
and Some ReactiorPof the Alkylchloride Derivatives of Phosphorus
with triethyl-phosphite. The chloromethyltrimethyl- and
chloromethyltriethoxysilane are analogously converted to
the trimethylailyle- and triethoxysLlylemetliylphosphinate.
In-the chlorination of tri- Cchloromethyl)-phosphine oxi-
de with phosphorus pentachloride tho tri- ("Irichlorome-
thyl)-phosphine dichloride was obtained, which in hydro-
lysis converted to tri-(trichloromethyl)-.phosphinehydro-
xychloride. This product can not be hydrolized and con-
verts with aniline to the oxide of the tri- (trichloro-
methyl)-phosphine.
There are 6 references, 4 of-which are Soviet.
SUBMITTEDs January 25, 1957-
Card 3/3

AUTHORS: Yakubovich, A. Ya, Ginsburg, V. A.
TITLEs On the Interaction Between Hydrazine and Carbon Disulfide
(0 vzaimodeystvii gidrazina s ser'ougle,-odom)
Experiments for the Synthesis of_Diico~hiocyanogen (opyty
sinteza diizorodana)
PERIODICALi Zhurnal Obshchey Khimii,1958,Vo1.28,Nr 4,PP~1031-1035 (USSR)
ABSTRACT: One of the authors formerly has shown -that according to
modified method by Kaluz on certain condtions alkylendi-
isothiocyanates can Ve obtained. In this work the authors
synthesized by analo~gous methods the simplest representa-
tives of thin compcund series -, the dilsothiocyano.gen
SCN-NCS~ ', which was unknown hitherLo. The scheme of this
synthesis caa be represented as follow!j:
ITH2NH2 + 2CS2 + 2NaOH > (1111CSSNa )2 M
(N11CSSNa )2+ 2C'COOC2H5 (NII(1,33cooc2if 5)2 (2)
Card 1/3 (11)

On the Interaction Betweer- Hydrazine and Carbcn.Disulfida
Experiments for the Synthe!jis of Diisothiocyaroger,
'19 .28-11-39/60
(NIICSSCO2C 2if5)2 (NCS)2+ 2CO342C 2 H5OH
(III)
In the interaotion between hydrazine and carbon disulf1do in
aqueous alkali medium t-he dioodium salt of the hydrazine-
--bis---d2.th1Qcarbonic ac-id was obtained. In the reaction of
this salt with chlorocarbornl~ enter ant) phosaene the
correep-.,,nding dianhydr-~.d,,,s (1111CS2CO2C2 15) and (MICS 2)COCl)2
form. The dianhydride of the hydrazire-bis dithiccarbonic
and ethyl,,arbon.1-o, a:~J.d chari.-es in heatLng to 1500C into the
ethyl. carbonate of the 2 r..ditlii,)l--l.93,4-.tliiadiazole. The
at 2r b-
latter decompose3 0 C and forms Vie ethyl thiocyanate.
The formati~rj of di.isothioc.yanogen Is not otserved in this
case. Also In the decomposition of the dianhydride of the
hydrazine.-bio--dithioc-abon-'~,-. and chloro,,,arbon-;.c acid the di-
isothiocyanoger, was not obtained. It was shown that the
alkyl thiocyanogencarbortic esters decompoute in heating and
thereby form alkyl thiocyanateo. There are 9 referenceu,
1 of which is Soviet.
Card 2/3

79-20-4-39/60
On the Interaeflon Between Hydrazine and Carbon Disulfide
Experiments for the Synthesis of Diisothiocyanogen
SUBMITTED: January 25, 1957
Card 3/3

79~ Z!j -4 1,10160
AUTHORS s Yalvabovirh, A. A. ; M:tkarcv, & P. , Giraburg, 7. A.
TITLEs A Froducz.1-or. Method for Fluorino Darlvatuive3 i~f the Organ-,
metal Compounds rf Silicoyi., Tin and Sulfur (Metod polucheniya
ftorproizvodnykh kramnlya, olo,.,a .1 sery)
FERIODICALa Zhurnal Obahchey NI: 4,PP-10,36-1038(USSR)
ABSTRACTt In the series of the alementorganio cor.pounds very often
alkoxy groups, which are bound +.:, the concerned elem nt, are
by action of acid chlorides exchanged for chlorine. The
possibility of the analogcns exchyAnSe .A' alkr,-v group3 for
fluorine by req-,tf.-on with arid fluarid-es has up to now been
investigated yet specAally. The xithor!3 investigated this
reacticr, at alko:qr compoixndEA J uilicon, tin and aulfur. On
P tba~ thc- uo'd `IvorideB of carboxyl-
that o,~caslon sh--~ved Q L
i-. acids.. idu particular the eagily ar_,.-tssible acfityl fluoride,
reac.t with the 9.lkoV comp,-~-jnds if t~.e named elements under
formatinr of tbP correep-ndi.-ig fluoridc,,4i
R EI(Da") CH 3COF P Uk EL(OF*)n F+CH 3COOR,
Card 1/4 The des-__rJteJ take.3 p"_t_~q i;astiir it' ttiEt central aton,

..,9 28-4-40/,,~U
A Production Method for F1;.,irjLrA Der'~vati-veq (;,t' ~:ie Organ:):Tle~al Compounds
of Silicon, Tin an2 5'alfur
to whil-h the 6r-,:,;.Y-,3 are t-urO , ~s an 31el-tropositive
element'. Thus cowp~~unds st t.7r_-, ex,,,har,02 the alkoxy
ero~.jps or, ;.f w~tn a:0.yj -1171u~,ride already
in the -oi,' frvr fiut-rtne. At, thte corre -pond I ng -_,ompounds
r.)f sili on and aa...27
a ~u-,: the exchange tak-t-) p ace at heating.up.
In all ~~aqen h,-Iq r_catrrunds fo:m, witb htgh yield,
By iC the r--_&,;'.Lcn partners in the
ca.-se r~,t only -)P~, but also a higher
numb~,r r~f L!:~ot.-rn ~.an be 3c,.. q,.e,, flom di-.
ethyldlethoxy tin ;-, tvnr. - and a difluurlda qan be obtained;
of tetraethoor;y T,.L:i ln -,-,aaa of surplu.,~ )f aoetyifluoride
easily for-as -sin
yl w'Q( aAk,:ixy slilansa was in..
The reacttion Df %,,et- A. I
.Wes~,-Aga-tr.,d at the axaraplo. of tetiab-utoKyeil,),ne. In this case
forms in case of heating up to '1800 tributoxyfluorsilane
with a yield, of 60 - '70 %o. The rea!iti~,,n of tetraethoxysilane
with benzoyl fluoridc, -#a9 in,~-etutlgated alrqady before by
Peppard, Bro7n and Johns,~n (Ref 2), b%t these authsrs could
not observe any exchange ;:~f the alko3ol Croups for fluorine.
Polyfinorsilanes cLra ~:,btalrod mo-r.- eapily by Grigrard's re-
Card 2/~, action from 9.11toon t47itrafl-aorld(~-., wt.l~h wns ob.4erved by

79-28-4- 10160
A Production Method for Fluorine Derivatives of the rjrgano=etP_l Conpc=ds
of Silicon, Tin and Sulfur
the authors already before in the synthesis of ethylsilane-
fluorides (Ref 3):
sip lufgx 3~ RSiF Rmgx I R Sill
4 3 2 2
The reaction of acetyl fluoride with a:,koxy compounds of sttlftjr
was investigated at the example of dimothyl sulfate, On that
occasion formed the methyl ester of the fluorsulfonic acid
with a yield of 60 % at conduction of icetylfluoride vapor
into boiling dimethyl sulfate. From the experimental results
comes out that the reaction of the carboxylic acid fluorides
with alkoxy compounds of various elements is a commonly
appliable important method for the synthesis of the con-
cerned fluorine compounds. As the initial products - alkoxy
-nmpolinds of the concerned 01CM3ntS end carboxylic acid
fluorides - in general are easily accessible compounde., the
described method earns general preparative interest.
In an experimental part exactly are described the synthesis
Card 3/4 and the properties of diethylethoxy t.Ln fluoride, diethyl tin

79-20-4--40/60
A Production Method for Fluorine Derivatives of the )rganometal Compounds
of Silicon, Tin and Sulfur
fluoride, tin tetrafluoride, tributoxy.rluorsilane, diethyl-
difluorsilane, ethyltriflaorailane, and of the methyl ester
sf the fluorsulfonic acid.. Thern are 3 references, 1 of which
JO soviQt.
IM"IT'M i Vebrijary 22, 1957
'lard 4/4

AUTHORSs
TITLE.
PERIODICAL:
ABSTRACTs
Card 1/3
Motoarevp Go V.$ Einglinp A. L.p 79-28-5-51/69
Yakubolai"A&,,I*,,,..~openskayaI is No
--Mro-val No Go
On the Catalytic Chlorination of
Ifethylahlorosilanes in theLiquid-Phase
(0 zhidkofaznom kataliticheskom khlorirovanii
metilkhlorsilanov)
Zhurnal Obahchey Khimii, 1958, Vol, 28, Nr 5,
ppr 1336-1338 (USSR)
The chlorination of organosilicon compounds in the
presence of azodinitrile of ioobutyrJ.o acid is not
described in publications. It was thorefore of interest
to try this method of chlorination in the synthesis
of chloromethylchlorosilane. It could be expected that
suen a chlorination of the methylehlorooilaneo had to
take place at the given chain mechan':em and had to lead
to the formation of all kinds of sublititution products
in the methyl group. It was actually found that in
chlorination on the given conditions (see table )" in

On the Catalytic Chlorination of the 79-26-5-51/69
Methylchlorosilanes in the Liquid-Phase
dependence on the mol ratio of the mothylehlorosilane
and chlorine.the whole range of ohlo:,-ine derivatives
CH 3Sicl 32 (CH 3)2S'C'2 and (CH 3)3 SiCl with the chlorine
atoms in the methyl groups can be obtained as is the
case in the photoehlorination of the methylehlorosilanes.
As it must be taken into account that the chlorine of
the methyl group of silane increases its further
substitution velocity in chlorination, the catalytic
liquid-phase chlorination for the purpose of the synthesis
of the monochlorine derivatives must take place in such a
way that a sufficient amount of the methylchlorosilane
which had not entered reaction remains. Thus -the reaction liquid-
phase chlorination of methylchlorosilanes- CH 3Sicl 30
(CH 3)2S'012 and (CH 3)3 SiCl was inveGtigated in the
presence of azodinitrile of isobutyric acid and it was
found that in this case, dependent on the mol ratio of
silane and chlorine, a whole number of chlorine derivatives
Card 2/3 containing chlorine in the methyl g:.,oup can be obtained.

On the Catalytic Chlorination of the 79-2B-5-51/69
Mothylahlorouilanen In tho Liquid-Phase
There are 1 table and 7 referencesp it of which are Soviet.
SUBMITTED: September 8, 1957
0
Card 3/3-

AUTHORS: Yakubovich, A. Ya., R%zu=ovskiy, V. V. SOV/79-28-7-45"4
Rozenshteyn, S. M.
Lna,
TITLE: Synthesen of Vinyl Monomers (Sintezy vinilovykh monomerov)
III.On the Syntheses of the VinyleoterE From Acet- and Chloro-
mercuroacetaldehydes, and on the Mecharism of These Reactions
(III.0 sintez.%kh slozhnykh vinilovykh cfirov iz zataet-i khlor-
merkurati3etalldegidov i mekhanizme etih:h reaktsiy)
PERIODICAL: Zhurnal obahchey khimii, 1958, Vol 20, Nr 7,
PP 1930 - 1936 (USSR)
ABSTRACT: The method of the reaction of acetaldetiyde with the chlorine
anhydride of the correoponding acid in the medium of a tertiary
base described by A.M.Sladkov and G.S.1'etrov (Ref 1) could
not be proved by the authors in any cave. In using pyridine,
for instance, neither the vinylbenzoate., vinylacetate nor the
vinyl enters of butyric-, caproic- or chloroacatic acids were
obtained although the conditions mentioned in carrying out the
reaction were strictly followed. Besides, the cryntalline de-
Card 1/3 positions occu=hig in this reaction are not mentioned. The vinyl

Syntheses of Vinyl Monomers. III. On t~,,e Syntheses of SOV/79,28-7-45/6-1
the Vinylenters From Acet- and ChloroMercuroacetaldehydes, and on the Mfecnanism
of These Reactions
esters of the phosphoric acids could be obtained by the reaction
of the acetaldehyde with their chlorinn anhydrides in the
presence of triethylamine (Ref 3)) the yield of vinylbenzoate
amounting to 15% (Ref 3). In view of these facts another method
of synthesis was tried (Ref 4) according to which the vinyl esters
of a series of acids could be synthesi:~ed in good yield3. Con-
cluding the following results nay be stated: In the synthesis
of the vinyl esters of the carboxylic acids from acetaldehyde,
acylehloride and pyridine only the chlorides of a-acylo;ryalkyl-
pyridinium could be obtained, In using triethylamino (inotead
of pyridine) with benzoylchloride a vinylbenzoate (yield 15,",')
was obtained, By the direct coupling or the halogen anhydrides
of the acids to the aldchydes the following compounds were
synthesized: a-chlorethylacetate, a-chlorethylbennoate,chloro-
methylmethacrylate, bromomethyli-iiethacrylate, and a-chlorethill-
methacrylate., This reaction is of 4,eneral preparative charrictcr.
By the reaction of monochloronerciiry acetaldehyde with the
Card 2/3 halog-en anhydrides of the' acids the vinyltr'Lfluoracetate and the

Syntheses of Vinyl Monomers. III. On the Syntheses of SOV/79-28-7-.15/64
7
the Vinylesters From Acet- and Chloromercuroacetaldehydes, and on the Uechanizm
of Thece Roactiona
vinyl-p-cyanobenzoate were synthesized. There are 20 reference--,
.8 of which are Soviet.
SUBMITTED: June 3, 1957
1. Vinyl esters--Synthesis 2. Acetaldetxyde--Chemidal reactions
3. Chemical reactions--Analysis
Card 3/3

AUTHORS: Yakubovich, A. Ya., Bogoalovskiy, N. A., SOV/79-28-8-62/66
TITLE: Syntheses of the Vinyl Monomer
(Sintezy vinilovykh monomerov)
:,
IV. Fluoro-Substituted Acrylat (IV. Ptorzameahchennyye akrilaty)
PERIODICAL: Zhurnal obahchey
khimii, 1958, Vol. 28, Nr 8,
pp. 2268 - 2291 USSR)
(
ABSTRACT: The number of the fluoro-substituted acrylates known is small (Ref
1). The authors synthesized an entire series of fluorinated
acrylatee. Starting from 0-fluoroethyl alcohol and 1,1,1-tri-
fluoroisopropyl alcohol and the chloroanhydride of methacrylic
acid they obtained by ordinary synthetic means the trifluoro-
isopropyl and P-fluoroothyl methacrylat*v (these are only
mentioned in the patent, but are described in detail in the
experimental section). The*attempt to synthesize fluoro-
methacrylate by replacing the halogen atom in chloro- or
bromo-mothaeryla.te with fluoride from potassium fluoride
was unsuccessful. Attempts to use the synthesis described
in reference 5 *ere also unsuccessful. Of those acrylates
which have fluoride in the acid part.of the molecule the
Card 1/2 authors synthesized the methyl-a-fluoromethylacrylate

Syntheses of the Vinyl Monomers. IV. Fluoro-Substituted SOV/79-28-8-62/66
Acrylates
and the a-difluoromethylacrylate and their derivatives.
The synthesis of these compounds was carried out according
to the procedure already mentioned. All intermudiate products
(ayanhydrina, a-oxypropionio acid and ita asters) which
had fluoromethyl and difluoromethyl-groups were separated
and classified. The starting materials, I'luoroacetone and
difluoroacetone, were obtained by reacting ohloroacetone
and dichloroacetone with potassium fluoride in diothylene glycol.
There are 5 referencesp 2 of which are Saviet.
SU1311ITTED: June 3, 1957
Card 2/2

AUTHORS: _Jatub jzh,_Avj--ftzumovskiy, V., SOV/79-28-8-63/66
9y
Rozenshteyn, S.
TITLE: Syntheses of the Vinyl Monomers (Sintezy vinilovykh monomeroy)
V.Syntheses of the Cyano-Subetituted Acrylates (V.Sintezy
tsianzameshchennykh akrilatov)
PERIODICAL: Zhurnal obolichoy khimii, 19580 Vol. 28, 11r 0,
pp. 2292 - 2295 (USSR)
ABSTRACT: Among the great number of esters of acrylic acid and
methacrylic acid described in the literature the esters
of the cyano-substituted alcohols have been little inves-
tigated. The syntheses of the smaller nonomeric esters
(Refs 1-3) and their properties have been insufficiently
treated. The authors investigated theso esters at great
length and synthesized according to known methods the
a-cyanoethyl, a-cyanobenzyl and the p-oyanophenyl esters of
methacrylic acid hitherto not described. Also synthesized
as side products to these esters were the previously unknown
cyano-sub~tituted metylamide of methacrylic acid,
Card 1/3 CH .(CH )C01113CH CIT, by reacting methaerylic chloride with
2-" 3 2

-"41~
Syntheses of the Vinyl Monomers. V.Syntheses of the SOV/79-28-6-63/66
Cyano-Substituted Acrylatea
the free aminoacetonitrile in acetone; and the derivative of
a-cyanoacrylic acid, vinylidene cyanide and the methyl
ester of this acid. The methods SUgg03ted in the literature
were modified somewhat. The literatura data on a-cyanoacrylic
acid are very scanty and are given in only two patents
(Ref 7)- Methyl-a-cyanoacrylate was sjnthesized with the
help of two methods described in the patents. In one case
methyloyanoacetate and chloromethylac.rylate were used as
starting materials, while in the other case methylcyanoacetate
and formaldehyde were used (see both reaction diagrams).
Nevertheless, the monomeric methyl-a-oyanoacrylate indicated
in the patent was not obtained, but instead the reaction
gave a somewhat solid, partially polymerized product. In order
to obtain the monomeric ester it was necessary to warm this
product with phosphorous pentoxide in order to depolymerize it.
The second method is more practical &-id also gives better
yields of methyl-aLayanoacrylate. There are 11 references,
3 of which are Soviet.
Card 2/3

-s7nItheses of the Vinyl Monomers. V. Syntheses of the SOV/79-28-8-63/66
cyano-Subatituted Acrylateg
SUBMITTED: June 3, 1957
Card 3/3

"otsarev, G. V.,_Lc~Rboy2i
S07/791-20-1 c,-22/6o
TITLE: Palo-erction of Aromatic Silanon (Gaicid-irovl-niy.- aron,~:.-
ticheskikh silanov)VI.Synthesis and Properties of the
Chlorine Deriv-tives of p-(Trichloro-!'~~thyl)phenyl Txi-
chloro-Silane ~VI.Poluchcniye i evoyst*vc. !:hlorproizvodr..,'-h
P-(tri'--hlormetil)feniltrikl,.lorzi-1--irs)
PERIODICAL: Zhurnal obahchey khimii, 1958, Vul M Nr lo,
PP 2727 - 2732 (USSR)
ABSTRACT: Earlier ;he authors shloWed that the introdtiction of
the oriented methyl Group into the molecule of phenyl
trichloronilano lorda to a certain activation of the
aromatic nucleus (Ref 1). It ~Yaa of int~.-reat to find out
in which way other oriented grouDs in the moleu~ille
of phenyl trichlorosilane, as for CCl 3 and CF3
would react to its chlorination. The chlorina'ion
of p-(-6ric;',lcro-:net",Yl)phenyl trichlcrosilrtne and
P_(tri fluoro-methyl)phenyl trifluororil~--e wao carried
out for the first time. As it is the CCl Groul;
Card 1/3 is a meta-oriented aubstituent. As tLe meta-ori~,,,-,ted

Halorrenation of Arom~-,tic Silanes. VI.Synthenic and
Properties of the Chlorine Derivatives of
Trichloro-Silane
substituents bring the benzene nucleuc, into a passive
position it could be ex.-jected that the presence of two
meta-oriented subntituents in Para position in the
p-(trichloro-methyl)phenyl trlchloron~. lane would
deactivate it in r. hi3-h deCrev- Actua-ly the
of this silane takes place without ca-;r-lyst als() in
the case of a lon,,'er ;ction of excess chlorine at 190-420'
Mono- and dichloro derivatives were o)tained on
action of chlorine on p-CC1 3C6H4SIC15 in the pi-oi;eiica
of FeOl The derivatives of this compound that are
tri- ang*tetrachloro substituted in the nucleus could
not be maintained because of the cloavaee of the
C-Si bond. It was found that the monochloro derivative
of P-Ccl3C6 H4Sici3is a mixture of 2-chloro- and 3-chloro-
4-(trichloro-methyl)phenyl trichlorosilane.
P-CF3C6 H4SiF3does not react with chlorine even at
Card 2/3 boiling temperature and in the preserce of FeCl.,,. Methyl

Halogenation of Aromati7c Silanes. VI. Synthesis and SOV/79-26-lo-221'6o
Properties of the Chlorine Derivatives of
Trichl-oro-Silane
magnesium iodide yields the 4,41-di(trimethylailyl)tolan
dichloride with p -,CCl3C6H4SiCl 3' The table shows the
influence of the reaction conditions on the composition
of the products obtained in the chlorination of
p-CC1 3C6R4 Sici 3' There are 1 table ard 10 references,
4 of which are Soviet.
SUBMITTED: July 6, 1957
Card 3/3

- YAKUBOVICTI, A.Ta.; SMIRNOV, KX; WDOV, S.S.
Syntbeels of vinyl monomers, 7luoroacetylons, its preparation
and propertiee, Kh1m.nauka i prow. 4 no-4,55,1-552 159.
1 . (Acetylene) (MIRA 13:8)

5 (3)
AUTHOROt Muboviobf A. Yds~ W44rovv Q* V, OOV/79-29-6-71/72
TITLE: Letter to the Editor (Fistmo.v redaktslyu)
PERIODIOAL: Zhurnal obahchey khimii, 1959, Vol 29, Hr 6, p 210o (MR)
ABSTRACT: In our recently published report Zhurn%l obahchey khimii, 1956,
Vol 26, P 568, the synthesis and the properties of dichloro-
and trichlorophenyl-trichloro silanes have been described. When
repeating these synthesis using large quantities of initial
products, we found, that the isomeric mixture of the dichloro-
phenyl;-trichloro silane boils at-127-1300 (100 mm) and d 4 55229
n. 20 1-5652, and that the isomeric mixture of trichlorophenyl-
trichloro silane boilg at 112-1150 0 mm) and melts at 63-670.
When re-arystallized from ether the melting point is 76-69'. in
the described tests commercial phenyltrichloro silane was used,
which was rectified beforehand in a laboratory rectifying col-
umn; its boiling point was 790 (10mmj, d 20 , 1-3265, n 20 1-5241
20 p
in the'tests,, carried out earlier, the phenvl-trichloro silane
was obtained in the laboratory by organo-magnesium synthesis
from 3'C'4 and bromine benzene Cboiling Point 7N730 (7mm),
20
20

5 (3)
AUTHORS: Yakubovich, A. Ya., Motearev, 0. V. SOV/79-29-7-65/83
TITLE: On the Problem of the Catalytic Halogenation of Phenyltrichloro-
silane (K voprosu kataliticheakogo galoidirovanija feniltri-
khlorsilana)
PERIODICAL: Zhurnal obshchey khimii, 1959, Vol 29, Ir 7, pp 2395 - 2400
(USSR)
ABSTRACT: In previously published reports on the catalytic halogenation
of aromatic silanes (Refe 1-4) the authors indicated that the
Sicl3 group had the character of a meta-orienting substituent,
whereas later investigations showed the trichlorosilyl, group to
behave anomalously, with orientation to-yards the ortho- and
para-position. In connection therewith and with opinions given
in roferenoea 5-7 the authors oonsiderel it necessary to find
a now method of daterminlag tho structuro of the ohlorine and
bromine derivatives oftenyltrichlorosilane. R. A. Benkener
and A. Torkelson (Ref found that phenyltrimethylsilane was
split by bromine even under standard conditions in the follow-
ing manner: C6H5Si(C11 3)3 + Br2 ) C6H5Br + (CH 3)3S iBr. In
Card 1/3 the present paper it was shown that also n- and m-chlorophonyl-

On the Problem of the Catalytic Halogenation of $07/79-29-7-65/63
Phenyltrichlorosilane
trimethylailanes reacted similarlyo forming n- and m-chloro-
bromobenzene respectively in high yields as well as trimethyl-
bromosilane. On chlorinating phenyltrichlorosilane in the pres-
ence of iron to Give the monochlorophenyl derivative ' two frn--.
tions were obtained, boiling at 98-1070 and 108-5-1120 (11 MM)
consisting.of monochlorophenyltrichlorosilane according to ana-
lysis. Exhaustive methylation of the low-boiling fraction yield-
ed chlorophenyltrimethylailane. Bromine split this compound in-
to (CH 3'3 SiBr and.ohlorobromobenzene, a liquid orystallizing
at -~260. As demonstrated in the dia ram, the freezing point of
the chlorobromobenzene mixture (-269) wits Practically identical
with that of a mixture of 950% meta- and 5P/16' para-isomor (-25.7o)-
Infrared spectroscopic data indicated the same composition. On
splitting the higher boiling methylated fraction of chloro-
phenyltrichlorosilane, which correspond.?d to o-ohlorophenyltri-
chlorosilano (Ref 5), o-ohlorobromobenzone was obtained. Thus,
the structure of the product was verified as that of o-chloro-
phenyltrichlorosilane. From the above data, and from data given
Card 2/3 in the experimental part of the paper it followed that the

On the Problem of the Catalytic HaloGenation of S07/79-29-7-65/83
Phenyltrichlorosilane
chlorination of phenyltrichlorosilane in the presence of FeCl 3
proceeds with the formation of a mixture of m-, o-, and n-
ohlorophenyltrichlorosilane at a ratio of 75:21:4t which is
consistent with data given in referenda 5. These results again
confirm that in the above reaction the 301 3 group behaves
anomalously, orienting towards the ortho- and para-potjition.
There are 1 figure, I table, and 15 refG::ences, 9 of which are
Soviet.
SUBMITTED: April 141956
Card 3/3

Wlz?~~TVIH ftXilMR-14 MLUIZL.21~
AUTHORSs Yakubovich, A., Gogoll, V., Borzova, I. SOV/80-32-2-45/56
TITLEt Accessible Method for the Synthesis of Trifluoroacetic Acid
(Dostupnyy metod sintena triftoroukausnoy kisloty)
PERIODICAL: Zhurnal prikladnoy khimii, 1959, Vol XXXII, Nr 2,
PP 451-452 (USSR)
ABSTRACTs Trifluoroacetic acid is prepared from 1#1,1,3-tetrachloro-
propane. The different stages aret the preparation of tri-
fluorodichloroantimony, the fluorination of tetrachloro-
propane, the preparation of trifluoropropene. The wanted sub-
stance is obtained by oxidizing trifluoropropene using an
alkaline solution of potassium permanganate. The yield is 80$.
There are 10 references, 1 of which is Soviet# 5 American,
2 English, 1 German and I Belgian.
SUBMITTEDs June 6, 1957
Card 1/1

3/629/60/0()0/003/004/011
D202/D305
AUTHORS: Losev, I. P., Gordon, G. Ya., Smirnow,, 0. V., and Ya-
kubovich,_
TITLE: Polycarbcnate8
SOURCE: Vsesoyuznoye khimicheskoye obahchestvo imeni D. I. Men-
deleyeva. Uspekhi khimii i tekhnologii polimerov, ab.
3, Moscow, goskhimizdat, 19609 47-66
TEXT: An extensive survey of the above new thermoplastic materials~
based exclusively on Western work. The authors describe the start-
ing materials for preparing polycabonates, methods of synthesis,
properties and possible applications, stating that most of the
available data refer to products based on 2,2-bis (4-oxyphenyl)
propane and its homologues. 27 compounds of this series are cited
and their melting and softening points, structural formulae and me-
chanical properties are tabulated* There are 7 tables and 35 non-
Soviet-bloc references. The 4 most recent references to the English-
language publications read as follows: K. J. Thompson and K. B.
Card 1/2

3/62Y60/000/003/004/01 1
Polycarbonates D202 D305
Goldblum, Ind. Plast. Mod 10 no. 5, 40, (1958); H. Schnell, Ind.
Eng. Chem., ',51# 157, (195~~-' 0'. V. Schulz and A. florbach, Macromol.
Chem., 29, 1-20 93, (1959); B. F. Fildler W. F. Chrietopher and T.
R. Calkins, Mod. Plastics, 36, no. 8, 115: (1959).
Card 2/2

Nill
21 .1
flialgl-
ICE?
PEE v
Air
aim
rf ~' w0 4i
liql,

Fundamentals of Synthesis Technology (Cont.) sov14659
3. Catalysts 556
4. Flow sheets of the process 562
5- Synthesis products and their processing 569
V. Nitroparaffins [I.N. Sergeyevskiy and A.Ya. Yakubovich] 574
1. Properties and use 'of nitroparaffind- 575
2. Nitration of paraffins in a liquid phase 577
3. Nitration of paraffins in a vapor phase 578
4. Technology of nitroparaffin production 581
Ch, X. Synthetic Rubber (0.B# Litvin] 591
Synthesis of moncaers 592
I. Divinyl 594
1. Technology of divinyl production from ethyl alcohol 594
2. Technology of divinyl production from butanes and butylenes 597
II. Isoprene 617
III. Styrene 620
1. Production technology of ethylbenzene md styrene 621
2. Separation and purification of styrene 628
Carkitn

5,3400 77900
SOV/79-30-2-51/78
AUTHORS: Yaku.bo_v_ich,__A__Ya., Makarov, S. P.
TITLE: Synthesis of Vinyl Monomers. VII f-(Vinylethynyl)-
Ethanol and 7 -Hydroxybutyronit~ii .
PERIODICAL: Zhurnal obshchey khimii, 1960, Vol 30, Nr 2, pp 6o6-607
(USSR)
ABSTRACT: ei vinylaqetylene andetiqlene oxi'delnir
The reacti be tw
o
.
ammonia yi
~ded (vinylethynyl)-ethanol. (b;p.. 63-64 C
F
8
at
zrjn, nD = 1. 932) which on hydrogenation was con-
verted to n-hexanol. A similar condenstion of sodium

t
salt of acetonitrile with ethylene oxide In liquid
.
ammonia yielded ",/--hydroxy-butyronitrile
(b.p, 235-
240 0 C). Evidently the reactions are general and can
be used to obtain en-yn-ols and y-hydroxynitriles.
There are 4 references, 1 Belgian, 2 Soviet, and 1
German.
SUBMITTED: December 29, 1958 Card 1/1

5.34oo 7790-
SOV/~,'9-30-2-52/78
AUTHORS: Yakubovich, A., Grobman~j Ye.
TITLE: Synthesis of Vinyl Monomers. VIII. Alken.,rl Esters of
Trimesic Acid
PERIODICAL: Zhurnal obshchey khimii, 1960, Vol 30, N:f, 2, pp 607-608
(USSR)
ABSTRAM The artlele describes synthesis of triallyl trimesate and
trivinyl trime3ate. Trial~yl trimesate (b.p. 210-212 0 C
at 2 mm, n20 = 1 5230) wasIsynthesized b7 the authors by
i
treating tFimesyl
qhloride with allyl alcohol. Treatment
of trimesyl chloride with chlormercuriacetaldehyde gave
trivinyl trimesate which was not previously described
in the literature. While the triallyl ester Is a
liquid, the triviny-'- ester is a cryztalline solid (no
m.p. given). There are 6 references, 4 German, I
Soviet, and 1 U.K. The U.K. reference is: Brit.
Patent 754537 (1956).
SIJBMITTEDx December 29, 1958 Card 1/1

5/07 60/030/04/50/080
B00%o02
)I
L 1-9 Bazilevsk acrylic
t) h Ike IS.1 IL ',de of Uoth
k ~Vbo V 7 -- ~ ),onomers Ix. inhydr..
'kUTIjORS 'Vinyl
thesis 0
The 1-274-1276
TITLBI kOj CI 1960, VO" 30' 140' 49
hchey Uhl ridee 01 m3tha':'
1,,d an __ uoti;n of
Zhurnal ob L 4
the P
se for ~o
Vt,d to produce some c lie sold and
uthorS atte , abstgnO ry ,,. 'Lfter
Us'& go initial s' I of moths oula be W
TBXTS The May be the RcYlat'ol C, ide dja
to Soidoich k that Only nce of pyridinep the ,hyar rtiolla-
orxj_-K~!% was IcnowIl the pre0l' 0 (5 torr)o
.___-~Jymere in otherv in go of 35-65 iiapropo%ed an-
PO thS ran indicates the cOmPl3te 1. Tits ai
seetyloblo, tillation "'_So tomperstuvs )rYljG
a vacuum disnot even at This in and meths( a 1060
above ris'
c.tie aoid. considerab
not freeze9 Waride during the state fro, a 0 but 9, .1 between
t,ou of the 9 in 8, PU'f er jut at .28 9 in alcoho, methaerylic
B obtained d a freezing Po tallizatio~ formio 'and. te
hydri&0 'wa, product ha its reoTY8 dride Of odium forms
aoid. Thl" tages place during Mi%ea snhy by boiling
In thesis of the ef.
,estan .The syu-Barness (patents Of
ao,,.r ding to
S
car& 1/2
C~'

SeAl)
3/07 030/00710)5/mAx
so a I Y1%
A Pj 3 0
AOMRS~ morlia, 7, A wake-,. S. P. DO-. S. 3
L. ad ukb.,ieh, I..
ML21 rI..rL_t&oft of the With Uran r"-
Rwanda =-
PUZODICALt Zloormal ehb.b.y kblail. 1~60. 1-1. 30. No. 7. pp. 237t.2374
TMI oft %be U.Is of let.. 1-5. %be &be.. r:-Qti.. .
in . mapper "..sloe ..Goal % ::P.&rri.S out with
dilat. flueria. ia3h ".,V"
C"20F, aud I" a.. product* ..to ..Perat.d by distill.tio (*.of 1 .8
"Ilea &I -25~44.50c, the other at -4.8-4.7ac) in additica to a fouslior%tu
of u.4h..8.4 first product. a enlarl.s. &,x., to
.6 .1, 4 , Z cobalt* alkali 1y., do.. .01 separate nor Iodine
Id- solution. 1. easily ..%able I. erg-I.
-*Iveats, and dtffimltlj 22 star. .1%. .1 .... tary composition "A molecular
moldhl .~..Pqwwl 1. tho forgals C212W73- to Prob.,417
due to the fl.orlonAl- " axot-Atril.. a- be p ... Ibly represented by
CA" 1/~3
%be Loomerto f,,,,.L- (1). (11). (M)
Cyciva. CyCNIP. C~z ?z
It monfirm the or this product it. 1ftfr.r spectrum .68 a.-
d. art , r he C-3 a
4al" Thar. tan, ar.st .%I a t I.:! . a.. bacJ gre.p
16 :001. 117 law! of the C-31 Und. An iM1 ... 0 hand Sky be
14.tratching vilirsitt"m of the N.F."ad. 'be.. ro-It. ..4 furlb.r
"in date Ottf. 6) witat.4 %1t.% %to structure. (1) -3 (11) of
#1 ITU
IU: _ :., %. .1 ody-2:a t "stop I a ally, which fact 27f&kb t
rg~j ). Is yro-
or (11 .6@a. II a is .1. support.4 by It
too land$ to %be Infrared. which say be regar4*4 as dof6rzalic
vIbralt.. f . tbres-membered ring. The structure of the product% di--
ftes.4 a:; :0 %be a a The second product En
I at r,
the "1...2- ..I'll 111 1-9 at 0.1 t% &q. I -alkaline =MO4
0,141,0a* " 'a -,g"t - *1*262, , con""
to the formula C I I? . In It. Larrared spectrum ShOo szo absorption
%ando which on, J.3,milgood to %be J-P "I C-R hoods, and a bani group
appears mob is do. 1. C-? -ibratlono. All tb... properties indicate
card 2/3
that al. straftez:. product 1. that
rise" tbyl -is Ib# complex CB3C BP3 Irk
%-7 Marine. 36% of a..t.altr1l. ron.lam; unchanged. The yields of the
r1morInAtics rj4xa%v referred %a the Initial c.t.nitrilm oze %ho fal-
law
Lodi for C33CY) - 'I%- VY21F - 3%, C13CY21"2"2 - '-5%'
F;CS - ?%. The" are 12 -f.r.ao-oz I 3.,I.t..? 03. 3 British. 3 Cars".
neab, WW I rolsian.
3"MIrm I July 11 1959
Card 3/3

S/079/60/()30/007/036/039/Xx
BOO1/B066
AUTHORS: Yakubovich, A. Ya,, Englin, M. A., and Makarov, S. P.
TITLE: Fluorination of Silver and Potassium Cyanates
PERIODICAL: Zhurnal obshchey khimii, 1960, Vol- 30, Yo. 7, pp. 2374-2377
TEXT: The authors describe the heterogeneous fluorination of silver and
potassium cyanates. The initial cyanate was mixed with.calcium fluoride
and treated with elementary fluorine diluted with nitrogen at 25-550C. V/
The fluorination of silver cyanate gives carbonyl fluo:7ide COF, (72%) and -
carbonic acid (24,5%), No nitrogen-containing products were detected,
which may be due'to the conversion of cyano-nitride to elementary nitrogen;
it was difficult to confirm the presence of the latter because of the con-
siderable dilution of the initial fluorine with nitrogen. Silver cyanate
is quantitatively converted to silver difluoride. On fluorination of po-
taosium- oyanate, trifluoro mothyl-hypofluorite,CP3OF (80%), and nitrogen
trifluoride, NP (609;), were separated in addition to lootausium fluoride
and small quantities of ourbonic acid and carbonyl fluoride. The expected
Card 1/2

Fluorination of Silver and Potassium Cyanates S/079/60/;)30/007/036/039/XX
B001/B066
hypofluorite FOCN could not be detected in the fluorination products,
which may be explained by a further fluorination on the CaN bonds accord-
ing toFthe formula
2
), [FOC=_Nj P
MeOCiw,N- !OCF2NF 2] --!L-+ FOCF 3 + NF 3' This formu-
la is in accordance with the fluorination of potassium cyanate, but not
with that of silver cyanate. Thus, another formula had to be found for the
fluorination of the cyanates. The authors have previouEl found that in
the heterogeneous fluorination of the oomp.'.ex ICH 5CN*BF,,Ffluorine adds
chiefly to the C=_N bond to form CH 3Cr2NF2 (Ref. 9). TI.erefore, the above
fluorination takes place presumably accord,ing to the formula
F Np2] F2 4.
MeOC=_N -Z--2-), (MeOCF2 [MeOCF 31 + [NF] . As a result of
further conversion of the trifluoro-methylate of the motal, which is
formed asan intermediate, carbonyl fluoride or trifluoro mothyl-hypo-
fluorite may be formed. There are 12 references: 2 Sov:,et, 12 US, and
3 German.
SUBMITTED: July 1, 1959
Card 2/2

82678
3/07gj6o/030/000/001/008
B004/Bo64
LUTHORS: Yakubovich, A. Ya., Bogoelovskiy, N.- .9 Pravova2 Ye* Po.
__!Re`=yayevav Is N,P_Razumovekiy, V. .
TITLE: Synthesis of Vinyl Monomers. 11. The Synthesis of
a-Chlorohydroacrylates and a-Chloroacrylatee ?
PERIODICAL: Zhurnal obahchey khimii; 196o, Vol. 30s No. 8,
pp. 2496 - 2498
TEXT: The authors report on the following syntheses: a-chloro-o-hydroxy
propionitrile (I) from aqueous solution of allZIonit-Ilelby introduction
of chlorine gas at 160C.'The compound was extracted with ether. Yield:
38.5%. a-chloro-p-aoetoxy propionitrile (2) from I bf heating with
acetic anhydride and sodium acetate over the water bath (yield 55-8%)-
Methyl-a-chloro-p-hydrox3p propionate (3) by chlorinating methyl acrylate
(yield 23-5%)- Methyl-a-chloroacrylate 4) a) by droppln(~ 3 into a mix-
ture of H 2s04 and Cu2C12 (yield 74%) heated to 125-1300cj b) by dropping
3 into a mixture of P20 5 and Cu,C12 (yield 64%). a~chloroacrylonitrile (5)
Card 1/2
"P"

82678
Synthesis of Vinyl Monomers. 11. The Synthesis S/079/60/030/008/001/008
of ce-Chlorohydroacrylates and a-Chloroaorylates B004/BO64
by heating I with sodium bisulfate. Phenyl-a-chloroacrylate (6) by addi-
tion of triethyl amine solved in benzene to phenyl-aip-dichloropropionate
solved in benzenep filtering off of the triethyl amiy.e hydrochloride
precipitate, distilling off of benzene and the exceavive triethylamine.
fractionating the residue in the presence of phenyl-fl-riaphthyl-amine
(yield 49~)- In 6 the authors found the refractive index nD 20 to be
1-5325, They consider this value to be more correct ';ban that of 1.5808
given in Ref- 3. There are 4 non-Soviet references'.
SUBMITTED: July 319 1959
Caid 2_/2

IS1 0 0 C.0 001/D067 6z=
AVTBMS: clft.b.rt, V. A., P. . 1kMlUza_t-A-
;Ahl-A. A. K..
TITL11 2-ati.n of Wog.ftm. Nitrogen 0.1d.. and
Xthylontells, Mtraviolet Light Synthesis iri
D-00-p-mitine of Pollfluvrimat.4 aliphatic lit-*
Compounds
P3210--CLL- tb Met obwk.hy Xhlall. 1960. Vol. )0. So. 7
pV4 2409 - 2415
TJXT- 1. ec.tl.* of their earlier paper (Ref. t) the a-j sh."
studded the r..C"L!!o: f p:.1yfluor1u^t*d athylono *lit SO =4 haloCau in
altr.,Iol.t light They . =94 that asoalo eblorin* or bromine would
also last to the i-llva or P-W-C.ft nir.1 jC-;,-d.. In f.-t. the
ymotr &I gift orv-,Lichlom th7l.". 1.2-41fl.cm-
tM'20 ths,.'rusmlta In good, yield.. -his -pmund
Card 1/~
-et.Z., "I could -b* Isolated (-uo.;-.m--16 -Lntb-m-
Tablo). *xPerlcent* b-4, as had bass theoretically exp~ted, that
In .11 c-4-- the corrempoulL.C %isms* alk".s sure ukt.1n.1 in -f-
flet"s yields an Irradiation of the Cas, zlxt~s. 10 * Cl, or 30 * Dr.
.1 th polyfluorizat-A et1j'snos (much so
or ti-Illom, t"lou. at the ratio clefin : No s W 2 t 1 1 1/2)
(Table). These cospe-da he,. " latemai,e blue ..1or. -1 mr. stable
11 qat4s. lesid9s the* &I** the earr.spaudlue wIkjIm2* diballdoe as volt
$-RItmC" bolld. e-y.-As are .2-ay. s.;azt.d fr- the "act 1us,
:"~. Pro!aylly they ~ products of a partial oxidation G! the ftltro.o
"p-ads, To red..Ing %be nIt".. c.pounds obtained f, trifluore
thyl.n. by ..&a& of hydrogen 1*41d. th. cotr-pm.ding f uurid.. or the
ch2orv-dinvoro- "A sold! are formed
vhleh indicates the &dLItIon of the halogen to the CF2 group of the
olefta In the remotion, loat.sen SO. 2.1'. and ol.rin. The py"lyal. of
Card 2/~
the ClCF1C?2'O "A 102CF2 CF,10 nitro.* e.o;aunds 120-130* 71.1ds the
polyfl.ortnut94 thil.al.14.8 CICT,ZplN - CYCFCl and TOPICY - X
- CYCF902 , There oxv I Uble and 0 rmf.rsac--! 3 go-Let.
1 U. and 2 C.man.
3uzx==. Jun. 4. 1959
Card 3/)

3/07q,/60/05:j-.GT/015/C'0
00c, SWIfRO67 82XD
MUM I., Pr 1. F, RC~41 ...... W. P.
Vt..b.ror, T. L------------
S, P A. To.
3, 3 .
TITM Z.oxtlos of
rtt,1,ow,.1 syth..t "A ti of palrfl.orlawt.l
lit-* C"R.=48
F=lCDlCLL: :hu,rn-1 .1tabch-y Wall. 190, 701. 30. No. 7.
pp. 2AC6
I=Ti I& of the papers (lots. I-T) an th:t".otion. of
rA%mayl Wall--- with baloConat*1 ol*tkn. the authors udied the roac-
VIb. of 920~ w-Ith h.mj~ltr .. Near."A.
might kove fo*au espectod as 1, the cas@ with aeft-f2uorinat*d uoa~aturated
As to. -4z.. Z ;2_, V~A zt2tv -j"
otbjloa# at rvca liquid of color. 2-altro-1 .1 2,2.
19 ma,1114 torved, (Refs. 6.7). 3..iA.o this
mads, ;roftzt (yield. wc," than iQC) a 4Lttre derivative of Utr~fluom
card 1/3
.%by2-. bad . .-1l azoncts of zion-14.ollfl.4 hich -bellied, products 1 1
.0 to
=ad. 1. the a- say . thl.rin-cont.lal.4 tatr .It ca* **%;..nd
.
forsed frax 9,0 3-d triflearo-chlo" ethylene. Th: 'It~m.o coa;,cunls
eyathostseot Vy the authors and sea* vther scientists (lefs. 3.4.9). as
ther olyflu*rLna%*A sitroso oompecteds, ars, rather *table, and
4olow"! 1. the infrared sp.clrus the bitroe* coo;,oucid. obt.to.d
ffta 'kqtrwJI-rcw*tbyl-w, show characteristic fmquinales of the valence
,leratics. e: %b I.nds I - 0 4*4 C - I at 6.2 0, and 12.25 a which
practicalI7 &tree with the frequencies obsolved in anal~7-~A
h: J; lasonOCU f. 10). Thanowasnattretowcospoind. are turned 14 the Is-
f I jith .trafl r tr Lfl oro-chl,are ethylen. a. Jrmdi&-
zzon, :,-th 11 -1c, I h reduction - f the nitro-itroso ca.-
U U, ' t 1!0" Z d - yield. the acid fluoride of
Vs" with dxIndlo . It to other . I
'Itro-41fl "re-so,otohyd"asalz sell which was separated as oth.rato
(lOzCFzCKlFO). The structure of the nitm.nitro.* coa,-d Mch us.
obtained freer N,O. "A tt-t I-- ttt
Card 213
re-otlou the addition, of 1 203 takes plats In such a way that the oltroto
Creep 1. UMk.df:1.th the carbon tozi which Sea . higher l.etro. d ... Ity.
Them sm, 17 re r news: 4 Soviet and 4 G-rawn..
SUIUMED. June 4. 1959

GINSBURG, V.A.; ZI=TIN. G.Ye.; DUBOV, S.S.; MAKAROV, S.F.; YAKUBCVICH,
4. Ya.
Synthesis of asters of thioazoearboxylic acids. Zhur.ob.khim.
30 no.8:2689-2692 A 160. (MIRA 13:8)
(Azo compounds5 (Acids)

GIVSBM, V.A.; VASILIYLPVA, M.N.; DUBOV, B.S.; YAKUBOIFICII, A.Ya.
Reactions of phosphites with azo compounds. Zhur. ob. khim. 30
no.q:2854-2863 S 160. (MIRA 13:9)
(Phosphites) (Azo compounds)

PHASE I BOOK EXPLOITATION 3()V^984
X!mt*rnatlonal symposium Ott macromolocular chealstry. Mose
1960.
x*&hd=Lrodnyy simpoziua po lakulyarsor khI&11 SSSR,
11bakra. 14-18 IXunya 2060 1.; deklady I avtoreforsty.
3*ktalya In. (Intemational Sy=oslum an MaCrOmolecular
Choldstry Hold In Moscow, June l"la, 19602 Papers aid
3UXNL&riax) section In. Emoscow, lzd~vo AN 33--R, 19001
469 P. 55,000 copies printed.
Tech. ad. x P. 3. r-h1m&.,
3pa6scrLog Aseacyt The International Union or Plare and Applied
Chandstry. Commission an Kaoromolecular Cbeadstry.
PURMS: . This book Is lnt#nd6d for chemists Interested In poly-
Imarizatlan reactiont; and the synthesis of high Molecular
i--campounds.
CCVERAGZ1 This Is 300tion III of a multivoluate work contain-
In papers an m&*r=ol*cular chemistry. The articles In
general deal with the kinetics of polymerization rexatlons.
th* synthesis Of special-purpose pal-Tzars, e.g.. Ion *I- _-O-
change r*alns. a4milconductor materIals, *tc., methods or cat-
8.171LIng polymerization reactions, proportion and chemical
i--teractions or high molecular materials, and the *ffoota of
various factors on polymerization and the degradation or
Man molecular a, r undo. No personalities are mentloned.
Rarailencos given follow.the artialts.
bek, T. I., andi"U21110-r- (Poland). Chlorl-natlon or,
Phenol-Formaldehyd* Resins 27
Oprin, and A Ciocnatj (Rumanta).
i~==l LhAm-unapropyi E;hrm-.T-%olyvInyl Alcohol 34
Yakuborich. A.-Yu, 2-IL-Q201m. L-L-Lul-IARX~- Ye- M-
't'Y - - Rizerevat. -
y' a., t~h,*-c'.html..,~.on~verasniodnNs of Polyearbon3tes 44
tue ---
Vockdkin. A- A . X S Palldahtqn, and (USSR).
Chemical Interactiti :3,d M--cV&F5:s of the Azt.-va"ng Action
---ckfj)OQh1e Systems or Vulcanization
O_A. SAIrckozA. amd_M,.r_
Acid and PolyFlFy-F-
Alcohol T3
11z. and The Titter-
and Polyvinyl Chlor--de 79
Oavde~! ;h--?L A
a-1-2mta, BL-A,-r-n::%!A4LL'.
'of
USSR). T a
r:*Mcln-"d~uctor Properties 85
Mkas-4-A_ and L. ~ 1"G, (Hungary). C~amtlcal Properties
of 31polar Xon-Exclzangs Resins 93
I., and J. ftravloo (Poland). Zfftet of' the 3tr%ka-
to" of orgatnic Aurn-o-Con-p-o-un-da on the PropertLe a or Anlon
Rosins Pron- Polystyrene
Sal agjL_Z~K (USSR). The Problem of the Effect of the
BrRucture or lonitea on Ion-Exchange'Proce3soo Between
Zooltes and. Electrolyte 3olutions lC7
Be 'I A A and
par, 11 a (CS&R).
add Properties of Soo Aromatic Polymors 115
Troo-tyanskaya, To V I P Losay A 3,_jev1.-ni 3 B
xer.mov.. nd-w-lihen~-..
Coovtralons of rn-soluble Copolymers or Styrene 124
JAZdrP-%n. -T~ (Poland). Thermal Stability or 3~rongly hviao
Anion ~ftange Resins x%6

87528
S/0-79/60/03()./012/0'.2/027
BOOI/3064
AUTHORS: Yakubovich, A. Ya. and Volkova, Ye. V.
TITLE: Synthesis of Vinyl Monomers. XI'.'Reaction of Vinyl Acetylene
With Nickel Carbonyl: 1-vinyl cyclohexene-3-dicarboxylic
Acid-1,4 and Its Derivatives
PERIODICAL: nurnal obshchey khimii, 1960, Vol. 30, No. 12,
pp. 3972-3978
TEXT: The authors found already previously that in the reaction of some
alkyl acetylenes with nickel tetracarbonyl in alcoh)lio media, a-alkyl
acrylates form by the blarkovnikov rule. Thereforet In the reaction of
vinyl acetylene with Ni(CO) 4 in alcoholic media the formation of a-vinyl
acrylaten waa to be expected: 4CH2= CH -C -CH + Ni (CO)4 + 2HCl
COO11
I
+ 4ROH )4CH2_ CH -C -CH2 + Nici 2 + H2' The auth.ors, however, found
that instead of the esters, their dimers form. Esters of dicarboxylic acid
Card 1/3

87528
Synthesis of Vinyl Monomers. XI. Reaction of S/079,160/030/012/012/02-,'
Vinyl Acetylene With Nickel Carbonyl: 1-vinyl B001/B064
cyclohexene-3-dicarboxylic Acid-1,4 and Its
Derivatives
C8if1O(COOH )2 were the resulting :reaction products. B.,, determining the
paraohors LAbstracter's note- the coefficient P is moant in the empirical
~rd_2(d_ I)] Of the
formula M individual ester dimers and their dihydro-
and tetrahydro derivatives, the dimer was clearly idontified as a cyclic
derivative. Sincep however, the calculated values of this kind for
compounds with six- and four-membered cycles and the-r difference are
within the experimental error limit, the structure had to be chemically
confirmed. A number of chemical oxperiments shovied that the enter dimers
obtained which are formed in the renction of vinyl a(;etylene with Ni (CO)4'
are derivatives of vinyl cyclohexene dicarboxylic ac-*d, and that this
reaction into alcohol media is accompanied by the formation of the esters
of 1-vinyl cyclohexene-3-dicarboxylic acid-1,4 (I). n a paper (Ref. 3)
published after this paper had been finished, the atl:uoture of u-(4-
-carbethoxy cyclohexene-)-yl)-acrylic acid is wronglY ascribed to the
final product of the above reaction. This error is proven by the identity
of vinyl cyclohexene dicarboxylic acid obtained by the authors with the
Card 2/3

87528
Synthesis of Vinyl Monomers. XI. Reaction of S/079-/60/030/012/012/027
Vinyl Acetylene With Nickel Carbonyl: I-vinyl BOOI/:3064
cyclohexene-3-dicarboxylic Acid-1,4 and Its
Derivatives
acid obtained (Scheme 2) by aaponifying the dione condenoation product of
2-cyanobutadiene (Ref. 4). In the catalytic hydrogenation of the esters of
1-vinyl cyclohexene-3-dicarboxylic acid-1,4, 2 hydrogen atoms are added
to the latter in the first stage, and derivatives of 1-ethyl cyclohexene-
3-dicarboxylic acid-1,4 form. In the following, more difficult, hydro-
genation two further hydrogen atoms are added so that finally, derivatives
of 1-ethyl cyclohexane-1,4-dicarboxylic acid result. Esters, acid chlo-
rides, amides, and other derivatives described in the experimental part
were obtained from the acids. There are 9 references; 4 Soviet, 3 US and
2 German.
SUBMITTED: Januaryll, 1960
Card 3/3

8752-9
S/075/60/030/012/013/027
B001/B064
AUTHORS: Ginsburg, V. A. and
TITLE: On the Problem of the Reaction Betwe-an Aldehydes and
Trialkyl Phosphites
PERIODICAL: Zhurnal obahchey khimii, 1960, Vol. 30, No. 12,
pp. 3979-3987
TEXT: It was published in Soviet papers (Refs. 1-L) that in the reaction
between aldehydes and trialkyl phosphites the aliphatic and aromatic
aldehydes form esters of a-alkoxyalkylphosphinic aoids (Ref. 1), whereas
ap 0-unsaturated aldehydes form addition products in the 1,4-Position
(Refs-2, 3). The esters of phenylphosphinic acid react analogously
(Ref. 4): RCH-0 + (C2H 50)3P ~-. (C2H 50)2p(O)CH(R)OC2 H5 (1)
CH2=CH-CH=o + (C2 H50) 3P >(c 2H 50)2P(O)CH2_CH=CH0C2H 5 (2), The struc-
ture of the compounds obtained was mainly datermiiied by phosphorus
analysis and from the values of molar refraction except for the product
which is obtained by reacting trialkyl phosphite rith acrolein and from
Card 113

On the Problem of the Reaction Between
Aldehydes and Trialkyl Phosphites
87529
S/079j(,0/030/012/013/027
B001/B064
which phosphone propionaldehyde is obtained by hydrol:rsis. The authors
regard these data as insufficient. Proceeding from trIethyl-, tripropyl,
tributylphosphite, and some saturated and unsaturated aliphatic and
aromatic aldehydes the authors obtained a number of phosphorus compounds
(Table). The elementary analysis and the molecular weights of the products
obtained show that only the reaction products with aromatic aldehydes
(except for salicylic aldehyde) correspond to the structure shown in
scheme (1). The composition of the reaction product obtained from phos-
phite and acrolein corresponds to scheme (2). The conposition of the renc-
tion products of trialkyl phosphites with aliphatic aldehydes essentially
differs from those calculated according to scheme (1). The chemical,
hydrolytical, and spectroscopic studies of the products No. 2, 3, 4
showed that their hydrolysis products have the structure of scheme (3).
CH 3CH2 CH 2CHLOCH(OR)CH2 CH2 CH31PO(OR)2
cone. HM
CH 1H CH CH CH
CH 3 2CH2 CH(OH) P (OR) 2 3 2 2 (OH)PO(Oll)2 + CH3CH2CII2CHO+11011
Card 2/3

87529
On the Problem of the Reaction Between S1079j'601030101210131027
Aldehydes and Trialkyl Phosphites BOO1/EO64
According to this formula two different alkoxy groups a:ce bound to phos-
phorus and carbon. This was confirmed for products No. 2, 3, 4. Besides
thereaction products of trialkylphosphites with excess amounts of alde-
hydes (1 mole phosphite ; 2 moles aldehyde) also a certain amount of
higher-boiling products corresponding to formula (R0 )PORICHO is formed.
Thus, only the aromatic aldehydes (benzaldehyde) forg the ad4ition product
RICH(OR)PO(OR) in the reaction between trialkyl phosphites and aldehydes.
Acrolein adds irialkyl phosphite in the 1,4-Position. The aliphatic satu~
rated aldehydes form addition products of two or thre-a molecules of the
aldehyde: to one phosphite molecule. In the former ca3e the structure
R'CH(OCH(OR)R'1PO(OR)2 uas proven. There are 1 table and 11 references:
9 Soviet and 2 German.
SUBMITTED: July 31, 1959
Card 3/3

87530
B/07Y 60/030/012/014/02 7
B001 BD64
AUTHORSs Ginsburg, V. A. and Yakubovic~~
TITLEs Addition of Trialkyl Phosphites to Acrylic Systems
PERIODICAL: Zhurnal obshchey khimii, 1960, Vol. 30, No. 12, PP-3987-3992
TEXTa In continuation of earlier papers (Refs.1-4) the authors found that
the most simple ketones, such as acetone, do not react with triethyl
phosphite under the conditions studied. A violent reaction, however, takes
place between triethyl phosphite and diphenyl ketonc already in the cold.
This is not the case between triethyl phosphite and diethyl oxalate con-
0
taining two conjugate C-0 bonds even at temperatureE; up to 170 C .The
acrylates and methacrylates served as initial substE.nces when studying the
reaction of the trialkyl phosphites with compounds containing the carbony!
group in a carboxyl group conjugated with the C--.C bond. In these cases a tY
reaction was also possible in the conjugate C-C-C-0 system or in the
C-C double bond according to Refs-4 and 5. The reaciion of trialkyl
phosphites with esters of acrylic 0and metagrylic acLd was inhibited al-
ready at temperatures between 140 and 16o C in the presence of hydro-
Card 1/3

67530
Addition of Trialkyl Phosphites to Acrylic S/0791'60/030/012/014/027
Systems B001/3064
quinone which prevents the polymerization of the acrylates. On hydrolysisp
the main reaction products of triethyl and tributyl phoophite with methyl-
acrylate (colorless, transparent oils) form the same tribasic organ~-
phosphoric acid which is identical with the acid described in publica-
tions (Refs.6-8). The infrared spectra of the esters synthesized indicate
the presence of a carbonyl group. The spectroscopic data, the elementary
analysis for C,H,P,OR (three alkoxy groups), the mc,lecular weight, and
the comparison of the constants of the products obtained with published
data, clearly show that the compounds obtained are triethyl and tributyl
esters of phosphone propionic acids (RO)2P(O)CH2CH2CO0R (Refs.9,7,12).
Triethyl eater of phosphone isobutyric acid % )COOR is
(RO)2p'O)CH2CH(CH3
formeft in similar way by reacting triethyl phosphite with methyl-
methaorylate. In the reaction with acrylonitrile, the ester of the
nitrile of phosphone propionic acid (RO)2P(O)CH'C112 CN whose properties
correspond to those described in publication6 11 C:71 .9 4 1
I ) are formed. Thus
it was proved that the phosphites containing acrylic systems mainly react
with the C-C bond. It is assumed that the above reaction mechanism is a
Card 2/3

,37530
Addition of Trialkyl Phosphites to Acrylic B/079160/030/012/014/027
systems B001/3064
free radical mechanism. In the reaction between triethyl phosphite, and
methyl acrylate also higher-boiling products are formed. They consist of
two even three acrylate molecules which are added to one phosphite
molecule, p-diethoxybenzene is formed at the same time. V. S. Abramov,
G. Kamay, and V. A. Kukhtin are mentioned. Furthermcre, the authors thank
S. S. Dubov for the study of the infrared spectra. There are 26 references,
15 Soviet, 7 US, 3 British, and 1 Gerwan.
SUBMITTED: July 31, 1959
Cara 3/3

S/661/61/000/006/022/081
I)205/1)*'~:02
AUTHORS: Motsarov, G. V., Englin, A. L. and Yakubovich,
A.
TITLE: Liquid-phase chlorination of aliphatic and fatty-aroma-
tic silanes in the presence o2' azo-bis-i.90-butylnitrile
SOURCE: Khimiya i prakticheskoye primeneniye kremneort-aniches-
kikh soyedineniy; trudy konferentaii, no. 6, Doklady,
diskussii resheniye. II Voes. Konfer. po khinii i prakt.
prim. kremn'eorg. soyed., Len. 1958. Leningrad. Izd-vo
AN SSSR, 1961, 110-112
TEXT: Recently, dimethyl dichlorosilane was chlorinated in the
presence of azo-bis-iso-butylnitrile yielding 90% of (CH ).(Ccl
3 3
Sici2 and (CC1 3)'(CHC'2)S'C'2 These are of intorest as otarting
monomers for preparing special silicon rubbers. For preparation of
the hexacilloro-derivall-ive other conditions are necessary. The syn-
thesis of (C 6 H5).(CC13).SiC12 was achieved by the chlorination of
Card 1/2

S/66!/61/000/006/022/081
Liquid-phase chlorination D205/D302
06H 5)(CH3)SiC12' Ye. P. Mikheyev (Moscow), S. A. Golubtoov (Nos-
cow), V. F. Mironov (IOXh, AN SSSR, Moscow) and V. S. Chugunov
(IKhS AN SSSR, Leningrad) took part in the discussion concerned
with comparicon of tht; two methods of chlorination of dimethyl
dichlorosilane, tho one using azo-bio-ino-butyAlnitrilo aij tlio ill-
itiatior and the other employing light. Ye. P. Mikheyev considered
.light initiation to be usually more effective. G. V. Motsarev dis-
agreed.
Card 2/2

DUBOVt S.S.; GINSBURG, Y.A.). KADINA, M.A.; RODIONOVAI N,P.; RODKIM, S.A.,-
- FILATOV, A.S.; T.AKUBOVICH.. A-Ya-
MAKAROV., S.P.y -------
Appearance of the aso .group in vibration and electron a ectra.
Zhur.VKHO 6 no*51596-577 '61o ~KMA 14.- 10)
(Aso compoundo-Spectra)

, 1!qrIP-, 1 4*v
;~, -~Q IV-z~v -,W -S-~
,
YAKUBOYjg9,-A--L-"; SOLOVOVA, O.P.; DUBOV, S.5--, C[IFLOIK)V, F.N.; STEFANOV-
SKAYA, N.N.; GINSBURG, V.A.
Structure and polymerization of compounds containing a trifluoro-
vinyl group. Zhur. VKho 6 no.6,709-711 161. (MiRit 14;12)
(Vinyl compound polymers)

YAKUBOVICH, A.Ya.; STEFANOVSKAYA, N.N.; 14IXIIAYLOVSKIY, L.P.; FAYEWIjVI, S.L.;
, ---S-GEWO-VA, O.P.-, ROZEIISHTEYN, S.M.: GIINSBURG, V.A.
Structure and polymerization of compounds containing a trifluoro-
vinyl group. Zhur. VKhO 6 no.6:712-713 161. (MIRA 14:12)
(Vinyl compourxl polymers)

YAKUBOVICHP A-ya-; ZALY'SSKIY, V.yu-
jalysis with the USO of the TU 170
X-ray 3pectroscepic 21 filters, Zav.lab, 27
radiation awme and differential (MIRA, 14..6)
n9.6t713-720 161.
(X-ray spectr9ac9py)

~.YAVBO.F.#,_ A,Yas; GINSBURG, V,A.;* MAKAROV, S.F.
I
preparation of fluorine derivativeo of phosphoruzie Zbur.ob.1-him
31 no,5:1517-1518 Vq 161. (XIRA 14:3)
(Phosphinic acid) (Fluorine compounes)

22204
3/079/61,/031/006/005/005
D223/D305
AUTHORS: Yakubovich,-AtYa., and Rozenshteyn,S.,M.
TITLE: Synth,&s;La.qnd properties of trifluoroacrylic acid
PERIODICAL: Zhurnal obshchey khimii., v.31,no.6, 1961., 1995-2000
TEXT; The present work describes the'ayhthesis of trifluoro-
acrylic eaters by dehalogination of v. -chloro-?--b-o-no trifluoro-
propioliate.' The initial (f -chloro-f'-bromotriflucropropionic acid
was obtained by potassium permanganate oxidation of 2-chloro-l-
bromine-1, 1, 2-triflu6ropentane - 3 freshly synthetized form perf-
1~xorovinyl-;-chlor~de, propylene and bromine (Ref-r-.% P.Tarrant, E.G-.
Gillman, J.Am.~Cltem.Soc--, 76, 5423, 1954)'.
C F-BrC F CIM :1==C 11C1 1, Mtno' CF9BrCFC1C0011
-C113C0011
By direct esteri4ication of chlorobromotrifluoropropionic acid or
its chloroanhydride the authors obtained methyl, thiomethyl, ethyl
Card 1/6

22204
S/079/61,/031/006/005/005
D223/D303
.Synthesis and properties of trifluoroacrylic acid
and plienyl esters of this acid. Difficulties we37e encountered
during dehaloge nation with zinc of alkyl-,.(. -chloro-_-', -bromo-trif JU,.
oropropio'nate. It appears that when this reaction is carried out
in absolute esters, not containing alcohol, the halogens removal of
60-70~-, yields as a'main product alkyl- -. -ethyl-'I; -etoxy-trifluoro-
propionate together with smaller quantities of alkyl trifluo.-oacryl-
ate (l6% of propionate). The formation of alkyl ethyl etoxy-propi-
onate was.due to the reaction of residual ester vrith intermediately
formed alkyl trifluoroacrilate. -The perfluoro acrylic system shows
an unusual tendency to nucleophillic additions which is sho%,,,n in
the case of reactions with alcohols and phenoln which join to per-
fluaroacrylinitrite lande-r ordinary conditions and in the absence of
alkalic catalysts. (Ref 6: I.L. Knunyants, B.L. Dyatkin, Izv. AN
SSSR, OKhNt 1958t 648; Amer. pat 2443024; Ch.A. 42, 7786, 1948).
.This property of alkyltrifluoroacrylatesp as shown experimentally,.
rules out dehalogenation with zinc, as for instance methylchl.oro
bromotrifluoro-propionate in methanol yields trifluoroacrylate
Card 2/6

22204
S/079/61,/031/006/005/005
D223/D305
Synthesis and properties of trifluoroacryfic acid
Which reacts with methanol and the product obtained in Y-.-hydro-,.--
methoxy-trifluoropropionate. The bonding ot elements of alcohol
(alcoxyl and hydrogen) into the structure and forming alcoxytri-
fluoropropionate is governed by the nucle6phyllic nature of. this
reaction, proceeding toy,-hydropropioiiate.
CF2BrCFCICOOR+R,Oll+Zo -- jCr2=CFCOOJIj-
TOC&CF11COOR
Since alkyltrifl
even on boiling
etoxypropionate luring
formation of zin,t'-Uhl-orid.e.aiad
plexes with este4s,
rized than in frile
High activity ofifluorinated
Oroacrylate does not react with simple esters
~Jhen it is obvious that formatioa ofa(-ethyl
the dehalogenation reaction is due to the
bromide. These certainly form com-
and-C-0 bond 'of these complexes'is more pola-
eater which doe6 increase its nualeophillity,.
acrylates towards nucleophyllic add-,
Card 3/6

22204
S/079/61/031/006/005/005
D223/D305
Synthesis-and properties-of trifluoroacrylic acid
.itions, the polarization of C-0 bond of the ester complex are fur-
ther confirmed by the decrease of activation engrgy of ester ad-
dition, a reaction which proceeds well at 30-35 C. The nucleophyl-
lie nature of the reaction by which etoxyl and ethyl radicals are
-added, is also responsible for formation of.~-etoxytrifluo.ropropio-
hate.
I* F
op,c -ZI 87 1 S* ^0-0-Znct,
0 ZM=CtZ C=C-C - Cjff50CFjCF(CjHSjCOO2
I I 'OR
CZH5 F F
This new reaction of additions of'simple esters -,o fluorinbLted eth-
ylene compounds in the presence of zinc halide's deserves further
study. The correctness of the above stated mechanism of reaction'
and the role of complex formation of zinc halides and esters is
proved by experimental work. The moistening of ester used in the
dehalogenation reaction of chlorobromo-trifluoropropionate decreases
Card 4/6

S/079/61/031/006/005/005
D223/D305
~Synthesis and.properties of trifluoroacrylic acid
the complex forma-ti=s..due to higher water solution tendencies of
zinc halides and hence inaraasen the yield of all.-yltrifluoroacrylp.-
tes. In this way the formation of trifluoroacry:.ate;from methyl-
chloro-bromotrifluoro-propionate becomes ~he main reaction (yield
401,4v) and ethylatoxy-triflouro-propionate -'a bid,~ reaction.
CF..DrCFC1C/,P + Zn CF,=CFCOOn+ZnX2-11*o
\0R
The ability of tr,ifl=~oacrylate to polymerize with other vinyl
monomers is.given. In conclusion the~authors state: 1) By the
zinc dehalogenatl-'On of tt-i-ohloro-r--bromotx~ifluoropropionic esters
methyl-, ethyl-,'.phenyl-, and methylthiotriflu6roacrylates were
prepared and invd.stigated; 2) It was established that action of
zinc on alkylchl&obromotrifluoropropionate in the ester medium in
addition to the tormation of trifluoroacrylate, produces double
bondinS of esterwith the final formation of alkyl-cc-ethyl-1-
ethoxytrifluoropeopiona,te; 3) During dehalogenation of methylchlo'
Card 5/6

2
,
2204
S/079/61,1031/006/005/005
D223/D305
Synthesis and properties of trifluoroacrylic acid
robromotrifluoropropionate in methanol.*-.-methoxy -t~'-hydrotrifluo~-
ropr6pionate i; formed as a result of reaction be-;ween alcohol and
intermediately formed methyltrifluoroacrylate, 4)-~,, -chlor'o-'el-bro-
motrifluoropropionic acid and series of its product were syntheti-
zed and investigated. There are 6 references, 2 Soviet-bloc and 4
non-Soviet-bloc. The references to the English-language publicaticas
read as follows: A.L. Henne, Ch. J. Fox, J.Am. Ch(!m.Soc. 76, 479,
1954;'J.D.. Lazerte, D.A. Rausch, R.J. Kashar, J.D.- Par 'k, V%H. Pear-
lson,. J.R. Lacher, J.Am.Chem, Soo., 78, 56399 1956; P. Tarrant,
E.G. Gillman, J.Am.Chem.Soc. 76, 5423P 1954.
SUBMITTED: -June'3,'1960
Card.6/6

~IYAKUBOVI~CH A.Ya.; BELYAYI,;VA, I.N.
'Mothylolhalcmalonates. Zhur.ob.khim. 31 no.7:2119-2122 Jl 161.
(Malonic acid) (NIRA 3.4:7)

gK MIN
GINSBURG, V.A.; MAKAROV, S.P.; SHFAIIISKlY, V.A.;
PIUVEZEMTSEVA, N.Y.; MARMOVA, L.L.; KIR'YA-N, 13.V.; IME, A.L.
Oxidation, reduction, and disproportionation of polyfluonitrosoal-
kanes. Dokl. AN 5SSR 140 no.6:1352-1355 0 161. (MIRA 14:11)
1. Predstavleno akademikami I.L.Knunyantsem I P.I.Kabachnikom.
(Paraffins) (Nitroso compounds) (Oxidation-reduction reaction)

,-,I -ru
y1iial gM!vA-YA,4 I U
". -, :011.,. 0 L. L.
,,!Ilotolysir ,olyfluoronitrosoaLkInes, a
pre, , 07. .
lysis =d .dth nitror~en oxidae
reaction of nitroso COTI 'PO
3j~: 11)
IIX $r 161.
Dold. I 3SR )aemikOrl-
1. ProdstaveLenc, .,a(
Ilitroso comnounds)
~Ilitrogen oAde)

MAK.4ROV, S.P.; --YAYUDOVICII A.Ya - GINSBURGj V.A.; FILAWN, A.S.,- EWGLDI,
M.A.; P TSEIIA, N.F.-, PRIVEZENTSEVA, N.F.; NIKIFOROVA, T.Ya.
Reactions of polyfuorinated nitrosoalkanes with amines. Dokl.
AN SSSR 141 no.2:357-360 N 161. 041RA 14:11)
1. Predstavleno akademikami I.L.Knunyantsem i M.I.Kabachnikom.
(Nitroso compounds) (AmineO

YAKUBOVICH. A.Ya.; ZAYTSEVA, Ye.L.; BRAZ, G.I.; BAZOV, V.P.
Synthesis of 2,4,6-trialkyl- and 2,4,6-triaryl-l,),5-triazineB
from imnoesters. Zhur.VKHO 7 no.2:229-230 t62. (MIRA 15:4)
1. Fiziko-khimicheskiy institut im. L.Ya.,Karpovae
(Triazine) (Eaters)

S/063116, 07A02/)'L2/-j
A057/A 12105
AUMORS: Zaytseva, Ye.L., Braz, G.I., YqkuboXi" -A.Ya.,- Bazov, V.P.,
Patrova, L.G,, Gitina, R.M.
TITLE: 3ynthesis of nixed 2,)1,6-trialkyl-1,3,5-tt-inziries and polyrrnr
triazine compounds from iminoesters
FERIODICAL: Zhurnal vsesoyuznoSo khimicheskogo obshchestva Imeni D.I.
Mendeloyeva, v. 7, no. 2, 19052, 2)2 - 233
TCXT: In continuation of earlier expevimenta In whJch syrime-tric 2,4,6-
-trialkyl- and 2,4,6- triai-11 -subs ti. tuted 1,3,5-triazines vieve prepared by cycli-
zation of imlnocst~_-rs in the presence of catalytic quantltl(~s of their salts,
2,4,6- substituted triazines mixed in an analogous way werx- pivixtred by combined
cyclization with esters of different iminoacids in the pres,int investigation.
When the paper published earlier was already in press, it was observed, that
F. Schaefer, and G. Peters reported on the same subject [Ref. 2: J. Org. C'nem.,
26, 2778 (iq6l)]~. If a mixture of ethyl esters of imino acid and Imino butyric
acid are cyclisized in the presence of 6 mole% of the chlorohydrate of imino-esters,
a mixture of four substituted triazines is obtained, namel.- a) R = R' - CH3
Card 1/2

S/063/62/W7/002/041 2/3 14
Synthenis of mixed ...... AO 57/A I 'J6
(where R positions 4 and 6, and It' position 2 in the symag.-tric triazine), b)
I
R = C113, R' = n-C3H71 c) R = n-C3H7 , R CP , d) R R' = n- "A - Ille con-)posl-
tion of the mixture depends upon the propor~hn of the initial iminoesters. By
distillation over metallic sodium the pure esters b) -and c) could be separated
and their characteristics determined, 2,4,6-tris-( e-carboet.oxybuty l)-triazine
was synthesized by cyclization oLl the diethyl ester of mono-I.minoadipic acid and
specified. A structurized polymer was prepared by cyclization of the diethylester
of bis-iminoadipic acid. The polymr is a yellow, crumbling substance, not solubL-
in common organic solvents, but swelling In benzene. Ilie saToe polymer can be ob-
tained from dlbenzylester of bis-iminoadipic acid. According to the infrared
spectrum th,~ poly;vr contains triazine rings, and apparently C - IM groups. A
triazine polymer.can be obtained also by combined cyclization of diethyl est-er of
bis-imino adipic acid and ethyl ester of imino acetic acid. Mere air I table
and 3 references.
ASSOCIATION: Fiziko-khimicheskiy institut im. L.Ya. Karpova (Physico-chemical
Institute imeni L.Ya. Karpov)
SMUTTED: December 22, 1961
Card 2/2

YAKUBCYVICH, A.Ya.; ZAYTSEVA, Ye.L.; BRAZ, G.I.; BAZOV, V.P.
Syntheses iis 1,,3,5-triazine series. Part 1: ItelAration
of 2AP6-trialkYl (aryl)-1,3.,5-triazines from Iminoesters.
Zhur.ob.khim. 32 no.10;3409-34-17 0 162, (MIRA 15:11)
1. Fiziko-khimicheakiy institut imeni L.Ya. Drpova.
(Triazine) (Eaters)

za 01 32819
S/020/621/142/001/017/021
BI 03/B1 11)
AUTHORS: Ginsburg, V. A., Yakutqyichj-.A.-,Ya-~ Pilat,)V, A. S.,
Shpanskiyy V. A-;-Masovap Y00 S., Zelenin, G. Ye.
TITLE: Production2 pyrolysis, and photolymis of polyfluorinated &so
compounds of the aliphatic series
PERIODICAL: Akademiya nauk SSSR. Doklady, v. 142, no. 1p 1962, 68-91
TEXT: Further methods of synthesizing polyfluoro azoalk.anse (PFAA) and
their derivatives were elaborated. It was found that PFAA were formed:
(a) when reducing azoxy compounds by PC13 vapor in the vapor phase and
/PCl 3
in N2 atmosphere at 100-1500c: RfN.N(O)R f ) RfN-NR:t + POC131
(b) when oxidizing hydrazo compounds containing R fNH groups: (RfWC?3#
CF2H' and others)l these compounds are synthesized by reducing asoxy
compounds. Among others) the following were used as oxidizers of hydrazo
derivatives: Cl 21 Br2, nitric oxides, chromate mixtures, potassium
permanganate in acetic acidl (a) when fluorinating linear or cyclic
Carcl 1/5

Is P 62/142/001/017/021
Y~6S
Produotionp p'yrolysis# and ... BlORIO
zines by CoV3 in a carbon fluoride medium at 90-1200C, or by elementary
(diluted with N2) at -10OC; (d) when fluorinating nitriles of
polyfluoro carboxylic acids and HON in the vapor phase on CoF at
100-150oc- Some ?FAA derivatives were synthesized: (G*l by c9lorinating
in the vapor phase in ultraviolet light_(UV) at 3000C, or by fluorinating
hydrogenous azo compounds on CoF 3 at 50 800c;
R C12 RfN_XCHC1 COF3 and others;
f----3 Uvr 21 or RfN.NCH3 0 RfN-NCHF2'
(f) by the usual conversion of functional groups. The initial azo
compounds used in reactions (e) and (f) were obtained ty condensation of
polyfluorinated nitroso alkanes with the corresponding aminea. The
constants of the substances obtained are tabulated. PFAA are 7ellow
liquids or gases which explode when heated, but are much more stable than
their non fluorine-containing analogs. Pyrolysis; It was found that
hexafluoro azo methane was slowly pyrolyzed in a coppez tube at 400OC:
GYN.NCF ~Oy + CP C? Similarly polyfluorinated homologs of
5 3 2 3 - Y
hexafluoro azo methane also decompose. This decomposition can be used as
a method of synthesizing PFAA. At 600-700 OCj tetrafluoro methane, tetra-
Card 2/5

32819
8/020/621142/001/017/021
Produotionp pyrolysisy and B1031BI10
fluoro ethylene, and lamp black are formed among others. This suggests
the thermal decomposition of intermediate forming trifluoro methyl
radicals. The low temperature coefficient, EaOt a ,v5 koal/mole, proves
the chain radical nature of the 49composing reaction in a high ooncentra-
tion of azo compounds. The free radical nature of the PPAk decomposition
was also proved in their photolysis in UV: hexafluoro azo methane
decomposes to form perfluoro t'etramethyl, perfluoro ho:tamethyl hydraxins,
and perfluoro hexamethyl totrazine. Polyfluorinated haxsalkyl tetrs.zinos
are 'stable and do not deocapose below 350-40000:
(CF3)2N-N(0?3)N(C?3) N(ClF.3)2 -* (C'3)2N.N(CP 3)2 + 073 NONCY 3' When
photolyzing trifluoro and pentafluoro azo methanep sutatituted hydrazinos
and tetrazines were isolated.. Due to a a*~~-sp*ctromt.trio investigation
carried out by So S. Dubov and A. M. Khokhlova# and due to chemical
conversions, it was proved that the active free radical In asymmetrical
&so compounds of the CP 3NwNR type wao predominantly a4icumulated on the N
&to& of the azo group next to'the lose electrophilio group. The free
radical nature of the above PFAA conversions is prove4 by their reaction
Card 3/5

32819
S/020J62/142/001/017/021
Production, pyrolysis, and B103/BIIO
in UT in the presence of acceptors of free radicals. Thuss hexftfluoro
&so methane,, in the presence of chlorinep changes intc trifluoro chloro
methane, when photolyzed, and into trifluoro nitroso methane in the
presence of nitric oxide or methyl nitrite. The alipttatic-aromatic azo
compounds of the RfN WNC6H 5type are resistant to high temperatures and UV.-
Thus, PFAI show a general tendency toward homiolytic d-soociation into
free polyfluorinated radicals and into an K 2 molecule. Thus, e is
2
produced in the case of an electronic impact. Pyrolytic decomposition of
hoxafluoro azoxy methane at 250-3000Cj however, takes a different course:
$ V~
CIP3SON OF3 _~' C?3N: + C113fro -10 CF3U02 + Cy3N - CF2
1 -31, CF3NONCF 3-
There are 2 tables and 5 references: I Soviet and 4 non-Soviet. The
three references to English-language publications reg.d as follows:
Ref. 3: D. Clark, H. 0. Pritshardo J, Chem. Boo., 1,956, 21361 Ref. 4:
J. R. Dacey,. D. M. Young, J. Chem. Phys. , no 1302 TI 955)1 Ref - 5: J- 0.
Card 4/5

32819
S/020/62/142/001/017/021
Produetionp pyrolyoial and B103/B110
Pritohard, R. 0. Pritshard, A. F. Trotman-Dickenson, Chem. and Ind-p =9
5641 Trano. Farad. Soo.9 52, No. 6 (1956).
PRESENTED: June 1, 19619 by Academician 1. L. Knuny&its and M. I.
Kabachnik
SUBMITTED: June lg 1961
vle
Card 5/5

ro 2zoi
11-421(l
32839
3/020J62/142/002/020/029
B1061BI01
AUTHORS: Ginsburg, V. A., Yakubovich, A. Ya., Filatov, A. S., Zelenin,
--kiy,
V. A., Kctelinikova, G.
G. Ye., Makarov, S. P., Shpans
P., Sergiyenko, L. F., and Martynova, L. L.
TITLE. Heterolytio tran eformatione of polyfluorinaied azoalkahes
PERIODICAL: Akademiya nauk SSSR. Doklady, v. 142, no. 2, 1962, 354-357
TEXT: A number of heterolytic transformations of polyfluorinated azo-
alkanes'was discovered for the first time. The said azoalkanes, while
being highly resibtant to oxidizing agents, easily react with reducers
(HIP H2 S, H3P) in polar medin (ether, methahol) at low temperatures,
whereby the azo group is converted into the hydrazo group. Hexafluoro
hydrazomethano presents acid properties and is relatively stable in thd
solvate form in ether or acetone. The etherate reacts itith ketene, and
the normal diacyl derivative is formed as a result. Hydrogen fluoride
is readily separated from hexafluoro hydrazomethane und-3r the action of
bases:
Card

fleterolytic trannformations of...
32839
S/020/62/142/002/020/029
B106/B101
11CFs (C%HsNH)%C=N-N=C(,N
CFaN11 N C41f&S)2C -N-N=C (SCol Ish
Hexafluoro hydrazomethane reacts with aluminum chloride to form the dimer
of tetrafluoro formazine, and, if oxidized in anhydrous media
(KhTnO + CH COOH), it passes over to the intensively yellow ciz.1-form of
4 3
hexafluorazo methane, which readily takes the almost colorless trans-form
under the action of light, alkali lyes, or metals. In the reduction of
azoalkane's which contain the groups CF2Cl or RfCP 2' the corresponding
hydrazo compounds cannot be isolated, due to hydrolysis, The compound
,CF3NHNHC6H5 can be distilled in vacuo (b.p.560 C/1 mm Hg .), and passes over
to indazole under the action of hydrogen iodide. Under the action of
strong acids, the azo group of polyfluorazo alkanes is able to add one
proton which, in the case of asymmetric azoalkanest is added to the
nitrogen atom adjoining the more electronegative substituent. These
reactions take place'most readily in anhydrous hydrofluoric acid, %hereby
polyfluorazo alkanea are dimerized into benzidine derivatives. Poly-
Card 21;r_

32639
3/020/62/142/(X)2/020/029
Heterolyt,io 'transformations of... Bio6/Dioi
fluorinated azo ,compounds. are particularly sensitive to nu3leophilic
reaction rate with aminoo growo with the amino basicity,
,,reagents. The
and,the.reaotivity in azo,oompounde of the typQ CF N-HR drops in the
o.equencie. R- OP '> CP 2H >CH,.... With secondary amines, mercaptans, and
31
sulfinio acids# the azo ou inp ounds re act as follows;
14NR,
kNR
jC~&NHN(CPs)NRjj---,(RjN)jC -'N-.7.N(CF.)NR.:
)., -,: , '. - ~
CO; ~S
aN N
JCNNIHN (CPs), SRI CFINHNK SSR~,--t-A)"
R
QIOSO H'.
Fi~
CF&NHN
16" (CFs)SOAHsj-CFj NNjCFs)SOjQH
Theseconveinions probably begin with the formation of-a transition
complex of the type of a n-complex, o. g4, UF IIvNCF This aasumption
IINR
2-
the fact that the transition complex, in the reaction of
s,baoked by
hexaf luorazo methane with trialkyl phoopbiten, can be isolated under mild
card .3/,r,

-2
S/020/62/142/002/020/029~
leidr6l$,~io,*tra iio B1061B101,
Y~ rmati,048 of..
UCOF, from
pd-l.yf l.u6io 'alkyl- (aril) rhydrazi`~e Oarboxylio aoids CP 11 (R)
ij 'nuMb t ivativ a was obtain'ed
lvh~q~ a ei~ -of.jur her der
-4cFlN'(R).N
kdN%
CFjN
ei MN (R) NHCOF 'N .(R), NHCQN.HCsH.s..
SOCHI
-- CFjN (R) NHC0jCHs
.
7
licl.m.0
RNHNH3 + 2COs 4HF
Thj~e',ari' -1 tabl and'. 3. tef ore.neon .2 -Soviet. and. 1. non-SO'Vle't.
Academician and M. I.
:PRESENTED% June 1, 1961,'by,l. -L. ?Kntinyarits,
~Kabachnik, Academic.ian
-.SLTBMITTEb,:",,:,,,,- lune--*l,~ -1-961
Table4't,.- Coinpounds.'synthesized fgr,,ihe ~firFjt,timo.
Leijs~d powpou,nd; (b)*boil~ng ` 6int (c) zhel t ing point,~' (d) does n c't
p
Ae,lt%'~q.10w, 3Q0, C
Card