SCIENTIFIC ABSTRACT GOLUBTSOV, S.A. - GOLUBTSOV, S.A.

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• Collection: Scientific Abstracts
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• Release Decision: RIF
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• Document Creation Date: November 2, 2016
• Document Release Date: June 13, 2000
• Sequence Number: 10
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

GOIJJBTSOV, S. A.
1. V. TroC.Uiova, K. A. Andrimov and 6, A. Uolubtsov, "The v"ynthesis of
Trichlors ilane. 11
.Repoxt presented at the Second All-Union Confurence on the ~,hemistx-j and
r'ractical kplication t~C Silicon-Organic Compounds held in Leningrad from
25-27 September 195P.
1
Zhurnal prikladnoy Idiiiiiii, 1954 , Nr 1., I'-p 23F-240 055R)

ANDRIANOV, K.A.; GOLUBTSOX S.A. . TISHINA, N.H.; TRorimovk, I.V.
.
Direct syntheeis of phenyltrichlorooilane in a fluldised bed.
Zhureprlkl.khim. 32 no.1:201-207 Ja 159. OIIRA 12 s 4)
(Silane)

5.36oo '75687
SOV/80-32-10-36/51
AUTHORS: Andrianov, K. A., Golu Lt-q_rv,_I, A., Trofimova, 1. V.,
Lobusevich, N, P.
TITLE; Direct Synthesis of Methylchlot,osilanes In a Fluidized
Bed
PERIODICAL: Zhurnal prikladnoy khimil, 1959, Vol 32, Nr 10, pp
2332-2335 (USSR)
ABSTRACT: The present work was done In 1954-1955. The effective-
ness of the fluidized bed application was checked by
the synthesis.of methylchlorosilanes. The reaction
between methyl chloride and silicon was carried out in the
presence of a silicon-coppev alloy (20% Cu), at 4-5
atmospheres pressure. The reaction is exothermic and
needs to be cooled. Special apparatus was constructed
which included a cooling system. Dimethy1dichlorosilane
content was between 42 and 47% In the reaction mix-
ture. A schematic diagram of the apparatus Is given,
Card 1/2 where 1 is methyl chloride cylinder; 2 Js water bath;

Direct Synthesis of Methylchloroallane3 In a 75687
Fluidized Bed SOV/80-32-10-36/51
3 is valve; It is evaporator, heated with hot; water;
5 is rotameter, 6 Is reactor, 7 Is fAlter; 8 Is water-
cooled trap; 9 is valve; 10 is traps cooled with dry
ice and acetone. There are 2 figures; 2 tables; and 4
Soviet references.
May 15, 1958

00(g)
44 ~ S/020/N~111/01/025/060
AUTHORS: Golubtsovq So A#t B011/BO06
KATH&K-bv, K. A. , Corresponding Member, AS USSRp
Tishina, '9771=
TITLE: Reaction of Joint Phenylation of Trichlorosilane and Silicon
Tetrachloride
PERIODICALt Doklady Akademii nauk SSSR, 1960, Vol 131, Nr 1, PP 91-93
(USSR)
ABSTRACT: The authors intended to eliminate the side reuctions which
lower the yield to 40% theoretical phenyltrichlorosilane
(Ref 5), and at the same time tried to phenylate the silicon
tetrachloride formed in the reaction. They found that the
hydrogenation of silicon tetrachloride with hydrogen proceeds
,:r%tisfactorily, if the reagents are heated under the same con-
dA:ions as bring about the phenylation of trichlorosilane
(440-4600, 180 atm). The results obtained proved that it is
fundamentally possible to phenylate SiCl,, if it is first
hydrogenated to t-richlorosilanet and only then reacted with
Card 1/3 benzene. The hitherto unused hydroLren formod -no a by-product

68812
Reaction of Joint Phenylation of Trichlorosilane 3/020/60/131/01/025/060
and Silicon Tetrachloride B011/BO06
in reaction (1) was utilized for the first otnGe of this
process. For this purpose, the authors rez,.cted a mixture of
Sici 4' 06H6, and trichlorosilane (Ref 6) under the above-
~inentioned reaction conditions. The molar rvtio of trichlor(-
oilane : SiCl, was varied between 0.25 : 0.75 and 0.65 : 0-15-
It can be cc(-,n .,rorq figure 1 that the yield in pheiiyltrichl~:zc-
silane (i n I-,- -- -.11 per 100 Lr-mol of reacted trichlorocilane) ir.-
creases with content of 9iC14 in the reaction
mixture. This cannot be explained c;iq)prosrion of the dif,-
proportionation of trichlorosilene, ccciti-rin- ac a si_'c 1:-e-
action, since the yield in phenyltrichlcrosil,-%ne often con-
aiderably qxceeds 100 C;-mol per 100 [;-mol tri c'ilorosi lane.
This orove-1 that the phony1rtion proceedo accor"'ing to t,.e ill-
tended scherno (see scheme L;iven), tinder utili,..rl' tion of tlc.
hydro, A 0~11::Cd
ren forried in reaction (1). Tke incr L -
sure facilitates the first roaction, i.e. hydro,,enation. Vc-r
this reenon -Nn_1 ,roduct, xals (A
Card 213 tained in much hi,,her yiel(I then at nt-

68812
Revetion of Joint Phonylation of Trichlorosilane
a,
e
nd Silicon Tetrachloride
S/020/60/131/01/025/060
B011/BO06
mospheric pressure. The authors have thus proved that the
phenylation of SiCl with benzene gives sufficiently hif;h
4
yields even without use of metalorganie oompoundop if con-
ditiona are so chosen, that SiCl 4 is hydrogenated by hydrogen
to the internediate trichlorosilme according to reaction (2).
Trichlorosil,~mo then reacts with benzene and forms phenyl-
trichlorosilr%no, rcgonoratin~; hydro(,~cn. There nre 1 fit~ure
and 6 references, 5 of which i~ro Soviet.
"UIji-JTTED- November 5, 1959
C"'. r(1 V 3

S/661/61/000/006/003/081
D205/D302
AUTHOR: Golubtsov, S. A.
TITLE: Direct synthesis of organic chlorosilanes
SOURCE: Khimiya i prakticheskoye primeneniye kremneorganiches-
kekh soyedineniy; trudy konferentsii. no. 6, Doklady,
diskussii, resheniye II Vaes. konfer. po khimii, i prakt.
prim. kremneorg. soyed., Len.t 1958. Leningrad. Izdvo
AN SSSR, 1961, 24-25
TEXT: The need for a more economical design of a pro--eos for direct
synthesis of chlorosilanes is stressed. Two main problems are to be
solved. One is the possibility of regulating the composition of the
methyl chlorosilanes. The second is the design of new processes
for various alkyl- and aryl chlorosilanes (including products hav-
ing a functional group in the radical) based on by-products of the
direct synthesis or some other readily available raw materials.
There is much room for the USSR scientist in the fields of mecha-
nisms and kinetics of the processes and also in the field of pro-
Paring new catalysts.
Card 1/1

37753
~T- 3100 3/661/61/000/006/004/081
It I'a 50 D205/D302
AUTHORS: Trofimova, I. V., Andrianov, K. A., Golubtsov, S A '
Turetskaya, R. A., Belyakova, Z. V., Y-rk`usHe-~a-'-,--7-.M'.,
Lobusevich, N. P. and Luzganova, M. A.
TITLE: On the regulation a,f the composition of products in the
direct synthesis ofmethyl- and ethyl chlorosilanes in
a fluidized bed
SOURCE: Khimiya i prakticheakoye primeneniye kremneorganiches-
kikh soyedineniy; trudy konferentsii. no. 6, Doklady,
diskussii, resheniye. II VBes. konfer. po khimii i prakt.
prim. kremneorg. soyed., Len., 1958. Leningrad, Izd-vo
AN SSSR, 19610 25-27
TEXT: Regulation of the proceae is one of the main problems in
preparing monomeric organosiliaon compounds. The most inte=ting
results were obtained during the attempt to regulate the product
composition by varying the prel'ar6.tion procedure of the catalyst.
Card 1/ 3

S/661/61/000/006/004/081
On the regulation ... D205/D302
This method opens wide possibilities as can be judged from the ob-
tained data. Thus a synthesis carried out on ~ Si-Cu melt contain-
ing 15 - 20% Cu gave 6% CH 3HSiC1 2t 30 - 40% (CH 3)2 S'C'2 and 40%
CH3Sici 31 while the synthesis on a Si-Cu melt activated by cuprous
chloride gave 6% CH 3HSiC1 2t 55% (CH 3)2 Sicl,2and 25% CH3 S'ici 30 Fur-
ther modifications 'of the catalyst bring about further changes in
the composition. Preliminary ekperiments on the production of me-
thyl chlorosilanes from meth ' ' ere performed. Methyl dichloro-
.PLAP I f
silane can be prepared in tliis,way, with trichlorosilane and sili-
con by-products which can be-qtilized. For synthesis of ethyl
chlorosilanes other methodeor, reFulating the product composition
were employed: Preliminary treat -nt of the Si-Cu catalyst by va-
rious gases at elevated tempett es, dilution of ethyl chloride
by gases and activation of th-I
hyl chloride by minor additions.
The most interesting results were obtained with preliminary treat-
ment by air at 3700C. About 45% of diethyl chlorosilane was pre-
sent in the product using a catalyst treated in this way. Dilution
Oard 2/3

S/661/61/000/006/004/081
On the regulation .. D205/D302
of EtCl with HC1 and the introduction of 0.5 - 0.7% moisture in-
creases the ethyl dichloroailane content of diethyl dichlorosilane.
There are 1 figure and 3 tables.
Card 3/3 $11,4

37754
5/66 61/000/006/005/081
D205YD302
AUT11ORS: Lobusevich, N. P., Trofimova, I. V., Andrianov, K. A.t
Golubtsov, S. A. and Belyy, A. P.
TITLE: Influence of some metal additives on the activity of
ailicon-copper alloys in the synthesis of methyl chloro-
ailanes
SOURCE: - Xhimiya i prakticheskoye primeneniye kremneorganiches-
kikh soyedineniy; trudy konferentsii. no. 6, Doklady,
diskussii, resheniye. II Vses. konfer. po khimii i
prakt. prim. kremneorg. soyed., Len., 1956. Leningrad.
Izd-vo AN SSSR. 1961, 28-31
TTL-,XT: The influence of impurities commonly encountered in silicon
(Al, Fe, ca) and copper (Bi, Sn, Pb) on the activity of silicon-
copper alloys used in methyl chloroBilane synthesis was investiga-
ted. Two series of alloys were prepared: 1) From purified Si with
less than 0.2~ of impurities; 2) from Kp-/I(Kr-1) silicon with 2%
impurities. These alloys, notwithstanding the identical procedure
Card 1/2

S/661/61/000/006/005/'081
Influence of some ... D205/D302
of preparation, were entirely different in their activity. Thus,
the alloys prepared from the purified Si gave a much lower dimethyl
dichlorosilane yield than those made of the non-purified Si. The
average figures were 34.0% and 41.0% respectively. The introduction
of Al (up to 1.55), Fe (UP to 3%), Ca (up to 0.6%), each taken se-
parately, had very little influence on the activity of the alloys
prepared from purified and non-purified Si. The use of Kr-2 silicon
gives worse results. Pb and Bi have a strong detrimental influence
on the activity of the alloys even at a concentration of 0.01% only,
while the results obtained on the introduction of Sn were irrepro-
duc-ible. There are 9 tables.
2---Card 2/2

S/661/61/000/006/014/081
D205/D302
AUTHOR: Golubtsov, S. A.
TITLE: continuous synthesis of phenyl trichlorosilane
SOURCE: Khimiya i prakticheskoye primeneniye kreneorganicheskikh
soyedineniy; trudy konferentsii, no. 6, Doklady, diskus-
sii resheniye. II Vses. Konfer. po khimii i prakt. prim.
krerw.eorg, soyedot Len. 1958. Leningrad. Izd-vo AN SSSR,
1961, 85-86
TEXT: In 1958, an apparatus for the continuous synthesis of phenyl
trichlorosilane was put into production. Benzene and trichlorosilane
.are fed through a filter into a mixer which is connected via a coo-
ler and surge capacitor with a column for the absorption of outlet
gases. The mixture goes through filters and a high-pressure pump
into a 40 liter reaction column working under high pressure and el-
ectrically heated. The products are discharged through a series of
valves and a cooler into a receiver. The gases are led into the ab-
sorber and the products are collected in a capacity tank and from
Card 1/2

S/661/61/000/006/014/081
Continuous synthesis of ... D205/D302
there fed to rectification. Data of 4 runs ranging in duration from
1
45 to 98 hours are tabulated showing that the laboratory yields are
fully reproduced in continuous operation. Indications are that by
appropriate changes in the synthesis conditions a quantitative
yield of phenyl trichlorooilane can be achieved. There are 1 figure
and 1 table.
Card 2/2

37759
S/66 61/000/006/016/081
D205YD302
AUTHORS: Popeleva, G. S., Trofimova, I. V., Andrianov, K. A.
and Golubtsov, S. A.
TITLE: Study of'vinyl chlorosilane synthesis
SOURCE: Khimiya i prakticheskoye primeneniye kremneorganiches-
kikh soyedineniy; trudy konferentsii, no. 6, Doklady,
diskussii resheniye. II Vaes. Konfer. po khimii i prakt.
prim. kremneorg. soyed., Len. 1958. Leningrad. Izd-vo
AN SSSR. 1961, 90-94
TEXT: During the investigation of the reaction 3C.H 2 = CHU + Si
CH 2 = CHSiC13 it was found that the catalyst.prepared from preci-
pitated CuO, Si powder and a liquid glass binder was the most,ao-
tive. 3 methods of contacting were tried: (1) Stationary bed of
pelletized catalyst (2 - 3 mm pellets); (2) an agitated powder,bed;
Z3) a fluidized bed. The first method gave good results when using
anhydrous PeOl.3 as an activator. The second method allowed the low-
Card 1/3

Study of vinyl
S/66 YD 61/000/000'/016/091
D205 302
ering of the temperature from 460 to 420 0C. The vi 1 trichloro-
silane yield was 33% and the output 10 - 15 g/hour7kg of catalyst.
The third method resulted in a reduction of the contact time by
a factor of 12 and a corresponding considerable increase in tempe-
rature. The yield of vinyl trichlorosilane was reduced, as the side
reactions were enhanced, to -26c&. In contrast to the synthesis of
methyl, ethyl and phenyl chlorosilanes where the beat results are
obtained in the fluidized bed, this method does not provide the
contact times necessary for synthesis of vinyl chlorosilanes. As an
alternative to the above reaction, the reaction HSiCl 3 + CH2 =
= CHSiCl 3 + HC1 is proposed. This reaction was investigated, yields
of 65,1.' being obtained at 500 OC' with a contact time of 35 seconds.
In the synthesis of methyl vinyl dichlorosilane by the reaction
CH3 31HC12 + CH2 = CHC1-->CH 3(CH2 =CH)SiCl2 + HC1, the optimum con-
'0 0
ditions ensurin- a 55c~ yield were 540 C and a contact time of 30
0
seconds. Thus the condensation of hydrochlorosilanes with vinyl
Card 2/3

S/661/61/000/006/016/081
Study of vinyl ... D205/D302
chloride gives a simple continuous'method for preparing vinyl tri-
chlorosilane and methyl vinyl dichlorosilane. There are 3 figures
and 2 tables.
Card 3/3

S/66 61/000/006/019/081
D205YD302
AUTHORS. Tarasova, A. S., Petrov, A. D., Ancbianov, X. A., Go-,#
lubtso Ponomarenko, V. A., Cherkayev, V. G.,
Zadorozhnyy, N. A. and Vavilov, V. V.
TITLE: Continuous addition of hydrochlorosilanes to unsatura-
ted compounds
SOUPCE: Khimiya i prakticheskoye primeneniye kremneorganiches-
kikh soyedineniye; trudy konferentsii, no. 6, Doklady,
diskussii resheniye. II Vaes. Konfer. po khimii i prakt.
prim. kremneorg. Soyed., Len. 1958. Leningrad, Izd-vo
AN SSSR. 1961, 99-100
TTEXT: Por practical application of the addition reactions of me-
thyl dichlorosilane, ethyl dichlorosilane and trichlorosilane to
liquid and gaseous unsaturated compounds an apparatus was designed
and optimum conditions of synthesis were established. The chloro-
silane and the gas are fed into a reactor. The products are dis-
charged via a cooler into a receiver equipped with a reflux. Dur- V/
Card 1/2

Con-~.inuous addition of ...
3/66 61/000/006/019/081
D205YD302
ing the reaction the reactor and cooler are cooled by water, the
receiver and the reflux by brine. The arrangement was tested on
the reaction of ethylene with methyl dichlorosilane and ethyl di-
chlorosila4e. The experiments have shown that in the 35 - 2000C
temperature range the reaction is unchanged giving a 65 - 75%
yield. No by-products are formed and the output is high (,> 6 kg
of methyl ethyl dichlorosilane/hr/l of reactor volume). The pro-
cess is amenable to automation owing to its insensitivity to tem-
perature changes. There are 1 figure and 1 table.
Card 2/2

S-'-1)300
21421
5/191/61/000/012/005/007
B110/B147
AUTHORS: Golubtsov, S. A., Belyakova, Z. V., Yakusheva, T. M.
TITLE: Synthesis of P-ethyl cyanide trichlorosilane
PERIODICAL: Plasticheskiye massy, no. 12, 1961, 20 - 21
TEXT: The long heating in the synthesis of P-ethyl cyanide trichlorosilane
(I) according to J. C. Saam, J. L. Speier (see below):
HSiCl3 + CH 2= CH-CN 3SiCH 2CH2CN was avoided by working in a 0-5
liter autoclave. 53 g of acrylonitrile, 181.5 g of trichlorosilane, and
3.6 g of dimethyl formamide were heated for 1 - 2 hr, and the reaction
products fractionated. 2ptimum yield (go - 67%) of I was obtained by
1-hr heating at 80 - loo C. At 50 - 70 C 47%, at 110 - 1300C 53% yield,
only the P-isomer, was obtained. Rectification on a column (efficiency
= 15 theoretical plates) yielded a fraction with 3.2% of trichlorosilane,
2.7% of azeotropic mixture (11% of acrylonitrile and 89% of SiCl 4), and
81.3% of SiCl 4' The gases contained 84% of H 2' 9.4% of N2' 1.5% of acid
Card 1

21421
S/191/61/000/012/005/007
Synthesis of B-ethyl cyanide .... B110/B147
admixtures, and 5.1% Of CH3Cl. For the continuous synthesis of I (Fig.),
dosing vessel 1 was filled through opening 4. The reaction mixture is
pressed into the reaction vessel 2 (a spiral pipe immersed into water) by
N2 supplied through 5. Dosing valve 7 and connector 8 are placed between
1 and 2. The mixture passes from 2 into condenser 3. The condensate
reaches the receiving vessel 12. The noncondensed gases are carried off
through the throttle valve 9. By means of the continuous apparatus which
can easily be automatized, working is possible for a longer period under
steady conditions. Productivity of the reaction vessel per unit volume
increases by the twofold as compared to cyclic operation under pressure,
and by the 140-fold as compared to operation under atmospheric pressure.
There are 1 figure and 5 non-Soviet references. The three most recent
references to English-language publications read as follows: G. D. Cooper,
M. Prober, J. Org. Chem., Zj, 240 (1960); J. C. Saam, J. L. Speier, J. Org.
Chem., 24, 427 (1959); S. Nozakura, S. Konotsune, Bull. Chem. Soc. Japan,
?1, 322 T1956).
Card 2/3

27902
S/07 61/031/010/002/010
D227YD302
AUTHORS: Belyakova, Z.V., and Golubtsov S.A.
TITLE: Synthesis of some (chloro-organo) silanes
PERIODICAL: Zhurnal obahchey khimil, v. 31, no. 10, 19619
3178-3181
TEXT: Tri- substituted silanes in which a silicon atom is linked
to both hydrogen and a chlorinated organic radical Cl-R-Si(RI)
(RII)H are practically unknown in the literature. Such compounds
are of interest producing polymers having chains with alternating
silicon atoms and hydrocarbons. In the present work the authors
prepared chloromethyl-methylphenyl silane, chloromethyldiphenyl-
silane and chloropheny1methylsilane by reducing the corresponding
chlorosilanee with lithium aluminum hydride. In the case of chlo-
rophenylmethylphenylchloro8ilane the reduction proceeded smoothly
and the yield of ch-lorophenylmethylphenylsilane was 69.5 - 72%
irrespective of the order of addition of the reagents. The reduc-
tion of chloromethylmethylphenylchlorosilane proved more complex;
Card 1/3

S/07 1 31/010/002/010
Synthesis of some ... D227~DI970
302
when LiAlH4 was added to chlorosilane the yield of product was
83% and reduction of chlorine in the chloromethyl group was prac-
tically non-existent. When the order of addition was changed the
yield of chloromethylmethylphenylailane was only 56%. The most
difficult reaction occurred in the case of chloromethyldiphenyl-
silane; under optimum conditions, the yield of chloromethyldi-
phenylsilane was only 67% and that of methyl,-diphenylsilane 7%.
Experimental procedure: The starting materials were prepared by
reacting the corresponding dichlorosilane (chloromethylmethyl-
dichlorosilane or chlorophenylmethyldichlorosilane) with phenyl-
magnesium bromide under the usual Grignard reaction conditions.
The products of distillation were used in the reduction which
was carried out in ether, adding the reducing agent to the chloro-
silane. After completing the addition the mixture was refluxed
for 6 hours, cooled and decomposed with 5% HC1. The ethereal so-
lution was washed and distilled. Redistillation of the residue in
the case of chloromethylmethylphenylchlorosilane reduction yielded
chloromethylmethylphenylsilane b.pt.99-100OC/14 mm n D20 1.53261
Card 2/3

27902
S/07 61/031/010/002/010
Synthesis of some ... D227%302
d420 1.0485 MRD 50.49; MR calc 50.69. Cliloromethyldiphenylsilane
and chloropheny1methylphenylsilane were also prepared; their pro-
perties are: b.pt. 175-18000/15 Mm nD20 1.5842, d420 1.10899
MR D 70.25o MRcalc 70-46; and b.pt. 172-1800C/25 mm nD20 1.5795,
d4 20 1.0982, MRD 70-50; MR calc 70-46, respectively. There are
7 references: 3 Soviet-bloc and 4 non-Soviet-bloc. The references
to the English-language publications read as follows: H. Gilman,
G. E. Dunn, J. Am. Chem. Soc. 73, 3404 (1951); U.S. Patent
2027591 (1950): G. Russell, J. Org. Chem. 2191190 (1950); R. A.
Benkeser, D. Foster, J. ArA. Chem. Soc. 74, 5314 (1952).
SUBMITTED: November 14, 1960
Card 3/3

25480
15, P5 1 -7 S/020/61/139/001/'O',2/018
B)03/B226
AUTHORSt Andrianov, K. A.., Corresponding Member AS USSR, Savushkina,
V. I., Golubtsov. S., A,,, and Charskaya, B. A.
TITLE: Thermal condensation of dichloro silane with chlorob,-nzene
PERIODICAL: Akademiya nauk SSSR. Drklady, 159, no.. 1961, 91. - ()8
TEXT: The authors studied the thermal condensation of dichlor-1- 81.1ane With
chlorobenzene H,,SiC1 . C H'01--n H SIM HCl 50 ~c phenyl dichlrrc
2 6 2
silane resulting in the process. In addition to zeact:Qn (1), they
determined the substitution ol the second"hydrogen atom at sill-con b., the
phenyl group. In the pre3ence of -.he Mgh terr-peretureq uzed here, (610
7000C). substitution of the hydToej~n atom -it Ly ri ~blorine sit-ii
was furthermore to be expo,"VeJ. Ai A I'e311j_t 'A" tws
the following compounds are present among !he reactlon products: Dipheny"
d1ohloro silane and phenyl-t~i-hlorc zilane (optinium t(Aal yield togeth~_vr
with phenyl dichlorO 31lanet I.1; if j '/~I,); furciierm,'re. Llv~riz-z!ne N, (4), and
trichloro silane (3). The present study provos thrat the yield of individual
Card 1/ 3

480
020/61/f-'9/OO1/Oi2/018
Thermal condensation of dichloro.-, B105/B226
reaction products is, above all, depunident upon t empera Lure . Up to at-.out
640 - 660 0C (optimum temperature of reaction (1)) ~he yield of pheny'
dichloro silane increases up tv 411-7 ~~, and, with a i'urther temperature rise
up to 700 0C, it decreases to 12 The yi.~,Id o" phenyl trishloro silana
i-ncreases at 640 - 660 0C to 18--3 arid up to 7000C coritiallea in,~-,-easlng Lip
to 26 Vc. The yield of dipheny'l dichloro silarie first -increases Np to 12.4%
at 660 0C), at 700'C, however, decreases t'-I1 2LC) ~-. Theoe facts speak in
favor of a continuously inc-reasing rate of the reaction mentioned at the
beginning. For these reasons, silane and chlorosilare aze practically
entirely absent in the reaction products, and In the decomposition .)f
dichloro silane neither hydrogen (2) nor side reactions of the chlorination
of chlorosilane 'hydrides (3), (4) have been proved to develop. The au*~horq
consider it quite probable that part of phenyl trichloro silane forms
according to the scheme HSiC1 3 4 C6 H5cl---:)Ic6H5 Sicl3 ~ HCl (5). The rate
H SiHC1 C H cl----t(c H I Sicl + HCI (2"
of reactions (3), (4). and (5), C6 5 2 6 5 6 5 12 2
Card 2/3

2~80
S 02Y61/139/001/012/018
Thermal condensation of dichloro. B103 B226
'H Sici + C H Cl--->HSiCl + C R H SiHCl + C H Cl--~>C H SICI +
2 2 6 5 3 6 6 (3); C6 5 2 6 5 6 5 3
C 6H6 (4) increases more considerably than that of (2). At 6800C the
formation rates of rhenyl trichloro silane *qnd toward similar values.,
Formation of trichloro silane and phenyl trichloro silane can hardly be
explained other than by (3) and (4); 1,8.,, neither by disproportionationt
2H2Sicl 2--)1HSiC13 + H3SiCi (6) nor by decomposition of dichloro silanet
3H2SiCl~~ Si + 2HSiC1 3 + 2H 2 (7). Also, the formation of benzene can be
explained only by reactions (3) and (4), and not by pyrolysis of chloro-
benzene in a reducing medium. In special experiments conducted on this
pyrolysis, the authors found that the benzene yield did not exceed 9%
(in hydrogen medium) and 2.2 % (in silane medium),. On the other hand, in
the production of phenyl dichloro silane 55 - 60 ~ benzene formed~ Also
the small yield of highly boiling products in the production of phenyl
dichloro silane points to the unimportant part played by pyrolysis. S. A.
Platonova and T. A. Klochkova participated in the experimental part'of the
study. There are 3 figures, 3 tables, and 2 Soviet-lu-'-.~c references.

310621621000100610041008
B110101
AUT'HORS: i';orozova, L. P,, Golubtsov, S. A., Andrianov, K. A., Trofim-.,
Rn
ova, I. V YOrFozov,
TITLE.- Formation of alkyl (aryl) chlorosilanes in direct reaction
of alkyl.(aryl) chlorides with silicon. Communication 1.
Selectivity of silicon and copper catalysts, and formation
of methyl dichlorosilane
PE'RIODICAL: Akademiya nauk SSSR. Izvestiya. Otdeleniye khimicheskikh
nauk, no. 6, 19062, 1005 - 1011
TEXT: Production.conditions, precipitating agents, a~d promoters affecting
t'he telective activity of silicon and copper hydroxide catalysts in the
.Lornrition of methyl dichlorosilane and dimethyl dichlorosilane were studied.
6ufficiontly active catalysts can be obtained by using copper chloride and
cop.,,er nitrate, but copper sulfate gives completely passive catalysts.
Simiultaneous precipitation of copper hydroxide and zinc hydroxide (,-v254 by!
vicight) increases the selectivity of the catalyst. Sodium hydroxide (in
the formation of methyl dichlorosilane) and NH4OH or Na2CO 3 (in the forma-
Card 1/3

3/062/62/000/006/004/008,
Formation of alkyl ... B110101
tion of dimethyl dichlorosilane) were found to be precipitating agents
ffivoring the selectivity. The greatest effect on the selectivity of the
catalyst is that exercised by promoters after the precipitation of hydroA-
dest Thus afters introducing ZnC1 2 the yield of dimethyl dichlorosilane
reaches 60~d4 and after introducing la 2Sio3 that of methyl dichlorosilane
mposition of methyl chloride on copper catalysts
reachos 4521;. Thermal deco
at 360-38000 (contact time ~-10 s 'ac) was also studied. The hydrogen ohlor-
ide separated-iri this reaction considerably affected the formation of methyl
dichl-Drosilane. The following reaction course was suggested for the forms-
tion -of methyl dichlorosilanet
catalyst
~IiCl + carbon + hydrocarbons
3 CH C1
Si + IIC1 C if3SiHcl2
zii + 2GH Cl _7~0 CH ilsimcl + carbon +.hydrocarbons
3 3 2
The ontimumtemperature for synthesizing methyl dichlorosilane was found to',
Ue 3,56-330'C. J~t higher and lower temperatures, silicon tetrachloride,
Car'" 2/3

s/o62/62/000/00,6/904/608
Formation of alkyl ... B117/B101
trichlorosilane, and methyl trichlorosilane were mainly formed. There
are 4 tables.
6UX..ITTF.D December 19611
Card 3/3

40912
S11911621000101010051010
B101/B186
AUT!10113: Go-lubtsov,.L._ A., Popeleva, G. S., Andrianov, K..A&'$ Zaalavs?6
kaya,
T I TLE: Thermal condensation of trichloro pilitne and methyl dichloro
s~lune with vinyl chloride
PERIODIGnIL: Plasticheskiye inaosy, no. io,. 1962, 21 - 27
Ti..)~T% Thf.~ruial condensation of Vin I chloride with methyl dichloro Bilane
Ian YO), abd vinyl chloride with trichloro
into metilyl vinyl 'lichloro 31 e
sibine into vinyl trichloro ailane W) was conducted in a reaption.tube
of stainlo.is isteel under atmospheric pressure.and at 30 sec contact time#
..Optimum reaction conditions were determined, and -the o.ondensation mechanism
and theriT.191 decomVosition vierc studied. Resultst. The optimum tempetature
for synthesizinr (I) is 530 -540 OC, the yield is 75 - 800jo' as referred to
the re-tctinp mothyl dichloro silane. The side products are methyl trichb=
silane, butadiene, high-boiling products, and gaoes containing 2~ H
C2H41 4.' C2H 3C1, 21~', CH 4' and up to 4;4 C2H 5 The thermal deeomposit, d.a.-of,
Card 1/3

Therwal condennation ...
'3/191 62/000/010/005/010
Biol/B186
0 0
methyl dichloro silano,5 - in at 400 C and reachoe 2(Y;v at 570 C. Th e
paseous decomposition products contain 7')~ H 2and 2% CH 4* The solid
residue cont-jins 65;~ Si but no free carbon. A' radical mechanism is..
ansumed, :aj kho solid decompooition products catalyze the decomposition
of methyl tlichloro silrine. The optimum condiCione for_the.synthegis of II
aret a molar rntio H'JiCl 3 : C2H3Cl - 1 2 1.5 and 500' 520 C. The yield
is 70 - 75~4 as referred to the reacting Asicl 39 and 601/7o"referred to the
reucting vinyl chloride. If the ratio is reduced to 1 1 0.6, the tempera-
ture has to be raised to 560 - 5600C. A ratio of 1 j I yielded GT~ II u-ith
respect to t4biCl . The side products are equal amounts of SiCl (15 r
~- moles
per 100 g-moles 3HSiCl 3)and high-boiling polymers. The gas coniains %v H,
12~~ C211 49 j~c C211 6' the solid residue contains 10 - 50~ Si and 30 -.75%,
elemwntnry oFirbon. The thermal decomposition of HSIC1 in H Siol p and
3 2P 4
Ji sets in at 560 - 570 C. The effect of the reaction vessel wall on the
composition of thie reaction products confirms the radical mechani6m of
the reaction, A surface increase of the reaction veeael by Raschig rings,
Card 2/3

B/igi/62/000/010/005/010
Theri~,al condoosation ... B101/B186
increasoo tILe yiL-ld of AG1 and decreases the yield of*II. Purification
of the renction veunel with4alkali-also reduces the yield of It. ;I nitro-
ren oxiie addition of.2% reduces the yield 6f II to 43~ and igareases that
of ~Acl to 13;~.' In the reaction of II with HCI at 560 - 570 C, the gas
* 4
consists of 9N,, 11 with 7% C If There are 6-figures and 3 tables. The
2 2 4'1
roost important Englich-langus, e referencee-aret English Patent 752700
(1956), C. A., 51, 7402 (195751 US Patent-2770634-0956), C. A., 51 10560
(1957), Japan Patent no. 16 (1951),.Co A#t 52t,3673 (1958)-
3/3

ANDRIAMOV, K.A.; TURETSKAYAf R.A.; GOWBTSOV,, S.A.; TROFIMOVAp LV.
Formation reaotioxw of alkv4(aryl)chlorosilanes in the direct'
inter~ctlon of alkyl(iryl) cnlorides vith silicon. Report No. 12:
Effect of hydrogen chloride on the formation of ethylehlorosilms.
Izv, AN SSSIt.Otd.khim.naukao.10:1788-1794 0 162. (KRA 15:10)
(Silans) (Hydrochloric acid)

33921
5/079/62/032/002/006/011
(3 0 D204/D303
AUTHORS: Popeleva, G.S., Savushkina, V.I., Andrianov, K.A. and
Golubtsov, S.A.
TITLE: Interaction of the halogen derivatives of aryl chlorosilanes
with hydrogen chloromilanes
PERIODICAL: Zhurnal obshchey khimii, v.32, no. 2, 1962, 557-562
TEXT., High temperature condensations of methyl dichlorosilane (I) with
methyl chlorophenyl dichlorosilane (II) (reaction 1), methyl phenyl chlo-
rosilane (III) with p-dichlorobenzene (reaction 2) and of III with methyl
chlorophenyl phenyl chlorosilane (IV) (reaction 3) were investigated. Re-
action I was carried out with 1:lLmolar ratios of the reagents at 570,
600, 620, 640 and 670 0C, with contact times of 40, 50, 60 and 80 sec., in
stainless steel tubes and yielded a mixture of the ortho-, meta- and para-
isomers of bis (methyl dichlorosilyl) bengene (A). It was found that the
yield of A, under optimum conditions (640 C, 60 sec.), was 27%, calculated
with respect to I. The product then consisted of 60%, of the liquid meta-
isomer and 40% of the crystalline ortho- and para-isomers. Reaction 2 at
Card 1/2

33921
S/079/62/032/002/006/011
Interaction of the halogen ooo D204/D303
5500C, with a contact time of 40 sec., in silica tubes, gave IV in 34.6%
yield, (calculated with respect to III)j when the molar ratio of III to
the p-dichlorobenzene was 2:1. Reaction 3 was rarried out in silica tubes,
.0
at 650 C and with 40 see. contact time, with reagents in 1:1 molar ratio,
and gave para-bis (methyl phenyl chlorosilyl) benzene (B), in - 30% yield
(calculated with respect to III). The structure of B was confirmed by a
Grignard synthesis. Physical constants of the products and full exporimen- Vr
tal details are given. There are 2 figures, 4 tables and 15 references:
9 Soviet-bloc and 6 non-Soviet-bloc. The 4 most recent. references to the
F&glish-language references read as follows,,. British Pat. 752,700 (1956);
Ch-A., 51, 7402, (1957); Ch.A. 47, 3875* (1953)i Ch.A. 47, 3334, (1953).
SUBMITTED-. January 30, 1961
Card 2/2

5/079/62/032/003/004/007
V204/0302
AUTHORS: Trofimova, I.V., Lobusevich, N.P., Gol.ubtsov, S.A. and
Andrianovt K.As
TITLE: The effect of certain netallic additions to Si-Cu alloys
on their activity in the reaction reith methyl chloride
P;~RIQDICAL: Zhurnal obshchey khimii, v. 32, no. 3, 1962, 841-846
TZXT: The optimum amount of Cu and the effect of adding rietals usually
present in Cu and 3i on the synthesis of methyl. chlorosilancs were in-
vestigated, at 350-370 0C, under 4 atm, by a method described earlier.
Purified Si (total 11+Ca+Fe+Ti