SCIENTIFIC ABSTRACT ANDRIANOV, K.A. - ANDRIANOV, K.A.

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• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R000101410020-2
• Release Decision: RIF
• Original Classification: S
• Document Page Count: 100
• Document Creation Date: November 2, 2016
• Document Release Date: March 20, 2001
• Sequence Number: 20
• Publication Date: December 31, 1967
• Content Type: SCIENCEAB

119.- 1? 1? 0 0
67947
-5W SO'.120-130-1-20169
AUTHORS: _&ndrianov, K. A.9 Corresponding Member AS USSR, Zhdanov, A. A.
Odinets, V-. A*
TITLEs Chloromethyla~~on~of Aryl-aliphatio Disiloxano6. Synthesis of
Chloromethylbenzyldimethylohlorosilane and Its Derivatives
PERIODICAL: Doklady Akademii naulc.SSSR, 19609,vol 130, Wr 1, PP 75-78 (USSR)
ABSTRAM The authors proved that thp chloromethylation of the bentyl group
bound.to,siliaon can-be quooesefully used for the synthesis
mentioned in the subtitle (see Scheme). This reaction proceeds
well in fuming hydrochloric aoido Paraform is used as an agent of
ohloromethylation. The ohloromethylation.in the presence of zinc
'
chloride i
s aacompanied by.secondary processes. They form viscous,
nondistillable prqduate oontaining.diphanyl-methane groups (see
Scheme).Ihe iaolation;otpure chloromethylbenzyldimethylehloro-
'
silane from' the re
safien.mixture was attained by hydrolysis with
excess.' waterlwhile the itipiloxane'mixtu.-re was split by strong
sulfurio aa1d`.in'the,pre6eAoe of ammonium chloride (see Scheme).
The tQtal'yield In chloromethylbenzyldimethylehlorosilane was 60%
of'the benzyldimethylohlo3rosilane reacted, and 30 of the quantity
used respectively. Direct fractiQnation of the chloromethylation
'
Card 1/2 products purified with waterin the vacuum delivered
smaller

61
0~11J2
020/6 1/01/025/060
S/
AUTHORSs Golubtson S. A.y BO11/BOO6
A.ndr-iano-v-,--"P-, Corresponding Member, AS USSR,
Tishina,
TITLE: Reaction of Joint Phenylation of Trichlorosilano and Silicon
Tetrachloride
PERIODICAL: Doklady Akademii nauk SSSR, 1960, Vol 131, ITr 1, T)p 91-93
(USSR)
ABSTRACT: The authors intended to eliminate the side reactions which
lower the yield to 40% theoretical phonyltrichlorosilane
(Ref 5), and at the saine time tried to phenylate the silicon
tetrachloride formed in the reaction. They found that the
hydrogenation of silicon tetrachloride with hydrogen proceeds
r:p.tisfactorily, if the reagents are heated under the sane con-
diklons as bring about the phenylation of trichlorosilane
(440-4600, 180 atm). The results obtained proved that it is
fundai:icntally possible to phenylate SiCl 41 if it is first
hydrogenated to t--i chl orosi lane, and only then revcted with
Card 1/3 benzene. The hitherto unused hydrogren formed as a by-product

68812
Reaction of Joint Phenylation of Trichlorosilane S/020/60/131/01/025/060
nnd Silicon Tetrachloride B011/BO06
in roaction (1) was utilized for the first otn~,-o of this
process. For this purpose, the authors rei,cted a uixture (T
Sici 4 PC.H6, and trichlorosilane (Ref 6) under the above-
~ "i"t. -
~inentioned reaction conditions, The molar ratio of trichlorl'-
oilano . Sleli! was varied between 0.25 -- 0.75 and O-G5 : 0.15.
It can be coun, rom figure 1 that the yield in plionyltrich1cro.-
silane (in --,1 per 100 g-mol of reacted trichlorooilane) 4r.-
ere,--.ses with iricro;,.slng content of SiC14 in the rc.-~ct-ion
. I' e
mixture. This cannot be explained Liv)-prescion of tho Oif:-
proportionation of trichloro si lane, ac a niCc ioe-
action, nirce tho yi-eld in phonyltrichloro,--i1v no often con-
.-iderr.bly qxceeds 100 C-mol Per 100 C:-uol tric'ilorosilancl.
This i)roves that the phenylnlion proceedo Lcc(:,:,.-,.in-- to t:ie in-
tended scheme (see scheme C:iven), under utili,.,-.tion of the
hydrog-en Aforried in reaction (1). T,-.o incroa.,:cd j-rot,
sure facilitates the firot reaction, i.e. h3,dr(;,;,-cnv. Lion, Y~:r
this rooncn "henylt~-ichlorvoilvn2,1 I.. 1mv (A-
tained in ruch hi,,,-her yielrl thrn -; id:t"!
2/3

68812
Reoction of Joint Phenylation of Trichlorosilane 8/020/60/131/01/025/060
and Silicon Tetrachloride 13011/Boo6
'-I"NITTED:
nospheric prensure. The authors have thus proved that the
phenylation of SiCl 4 with benzene gives sufficiently hiCh
yields even without use of metalorganic compounds, if con-
ditiono are no chosen, that SiCl 4 is hydro,-,enated by hydrogen
to the intornediate trichloronilrne according to re.-.ction (2).
Trichlorosiln= then reacts with ben:ivne and for.-.s -ohon.-l-
trichlorosilrnc, rcgonorntinU hydro(;cn. There ,.re 1 fi,'ure
and 6 refol'('11COCP 5 of which -.ro Soviet.
November 5, 1959
C'~'x.(! '*/3

57. 51 69506
AUTHORS: Andrianov, K. A., Corresponding B/02 60/131/04/029/073
_jM=-Gr-'0Xff9M1 Kurasheva, N. A. B011YBO17
TITLE: On the Reaction of Titanium Tetrachloride With Rexamethyldisiloxanal
PERIODICAL: Doklady Akademii nauk SSSRI 1960, Vol 131, Nr 4, pp 825-826 (USSR)
TEXTt The experiments carried out by the authors have shown that the effect
produced by titanium tetrachloride above 100 0 causes a rupture of the siloxane bond
in hexamethyldisiloxane. In this conneotionp trimethylsiloxychl8ro derivatives
of titanium are formed. If this reaction takes place at 120-200 , only trimethyl-
chlorosilane and trimethyleilox-vtrichlorotitaniumq(yield 69.8%) are formed (see vkoo'
Scheme). All efforts to obtain products of higher degrees of substitution (i.e.
bie-(irimethylailoxy)-dichlorotitaniuR) failed. The latter compound# however, was
formed in a yield of 34.7% at 280-350 due to another reaction scheme (see this one).
This indicates that the halogen on the titanium atom is replaced by the second
siloxy group, probably due to the reaction of trimethylailoxytrichlorotitanium
with he-jamethyldisiloxanee Experiments carried out with these two substances at
280-320 yielded bis-(trimethylailoxy)-diohlorotitanium in a yield of 43.0%
(see Scheme). The mechanism of rupture of siloxane bonds during the reaction men-
tioned in the title proceedet according to the authors, in the following manner:
the titanium atom in TiCl4 is coordinated with the oxygen of hexamethyldisiloxane
Car

69506
On the Reaction of Titanium Tetrachloride With S/020/60/131/04/029/073
Hexamethyldisiloxane B011 B017
under formation of a transition complex M. The further process is accompanied
by the rupture of the siloxane bond due to the zedistribution of the electron
density. Titanium is added to oxygen, and trimethylchlorosilane and trimethyl-
siloxytrichlorotitanium (II) are formed. The addition of the seoond siloxy group
to the titanium atom probably takes place through the coordination of the titanium
atom of trimethylsiloxytrichlorotitanium with hexamethyldisiloxane (III). In the
followingt trimethylahlorosilans and bis-(trimethylsiloxy)-dichlorotitanium (IV)
are formed. There are 6 references, 2 of which are Soviet.
ASSOCIATION: Institut elementoorganicheskikh soyedineniy Akademii nauk SSSR
(Institute of Elemental-organic Compounds of the Academy of
Sciences, USSR)
Cazd=R2~1-

84671
S/020/60/134/006/014/031
B016/B067
AUTHORSi An ja&2X"4 Corresponding Member AS USSR Rnd
E5-veTinjj, V.-
TITLEa Tel.omerlzationlReaetion of Organo-cyclosiloxanes
PERIODICAL3 Doklady Akademii nauk SSSR, 1960, Vol. 134, No. 6.,
pp. 1347-1349
TEXTi The use of telomerization reaction in organosilicon compounds As
rendered difficult due to the lack of el.4DPnital-organic monomers with
double bonds between element and oxygenp and capable of polymerization.
The authors, however, effsoted the telomerization of octamethy! zyclo-
tetraell.oxane as cyclic oompound and di.methyl Sichlorosilane as a
substance effecting the rupture of the mclecular chain. Experiments
showed that, in addition, the former compound is polymerized by the
latter. The authors found that the reaction of the ring cleavage without
catalysts proceeds Tapidly at 200-2500C. At a ratio between the first
and the second substance of 2 s I it was completed at 2500C wit.bin
3 hours. Oligomers were obtained corresponding to the compounds of the
Card 1/3

Telomerization Reaction of Organo- S/020/60/134/006/014/031
cyclosiloxanes 13016/B067
following reactiong n(M 2S-to)4 + M2S'C'~~ C'-(-M2S'O-)4n'-M9S"'; (M-CH 3).
These results were reproduced by repeated experiments. In their expe.-i-
ments the authors obtained about 75% of' reaction produ-,ts which can be
distilled below 2600C at 3 torT; only 25% bo'-d at higher temperatures.
The following compounds were isolat,?A by rectifications cKgj-dichloro
decamethyl pentasiloxane (n - 1), yield 16-7%, rJ,oi-di.-hloro-o^-tad9,-,a-
methyl nonasiloxane (n 2), yield 20.0%, and (y,,r;--dichloro hexalcosa-
methyl tridecasiloxane n - 3), yield 7.7%. Table I gi-es the physical
properties of these products. The formatIon of .31igomc-rs with 5t, 9,, and
13 silicon atoms In the molecule indicates a succesBive addition of the
molecules of octamethyl cyclotetraelloxane to dimethyl dichlorosilane.
Apparently the.-reaction is initiated by the coordination ~f one of ths
oxygen atoms of octamethyl CyClOtetTasiloxane with the 941licon atom of
dimethyl dichlorosilane. Due to the weakening it the SI-O bond In the
former the strained ring Is ruptured with chlorine being added to the
silicon atom, whereas dimethyl dichlorosi2ane is added to the oxygen.
A
The further growth of the chain is probab17 dur- to the zoordination of
the silicon final at=e and the oxygen of the product. This Is
Card 2/3

Telomerization Reaction of Organo-
cycloailoxanes
84671
S/020/60/134/006/014/031
B016/BO67
followed by the rupture of the ring and the formation of a linear O(vO-
dichloro dimethyl siloxane. Ths'~-a presumable reaction mechanisms are
explained by scheme3. The authors continue the study of this reaction by
the example of similar cycles , and they investigated fu.-ther reagents
effecting the rupture of the molecular ohain. There are 3 tables and
II referenoess 4 Soviet, 4 US, I British, and I Japanese..
ASSOCIATIOM Institut elementoorganicheskikh soyedtnenly Akademii nauk
SSSR (Institute of Elemental-organio Compounds of the
Academy o Sciences. USSR)
SUBMITTEDs July 9, 1960
V/
Card 3/3

LUTHORS:
TITLE:
PERIODICAL:
86393
-3/02 6o/135/002/018/036
Bol 6YB052
Andrianov, K. A., Corresponding Member of the AS USSR,
and K-ur-a-sYe-va, N. A.
The Reaction of Heterofunctional Condensation of
Bis-(trimethylailoxy) Titanium Dichloride With
Phenyl-methyl Diethoxysilane
Doklady Akademii nauk SSSR, 1960, Vol. 135, No. 2,
pp. 316 - 319
TEXT: The authors studied the reaction of heterofunctional condensation
between bis-(trimethylailoxy) titanium dichloride and phenyl-methyl di-
ethoxysilane at 1500C. They found that not ethyl chloride, but trimethyl
silane chloride is split off under the formation of a polymer. The che-
mical composition of this polymer is given by equation I of the attached
scheme. The polymer is easily soluble in benzene and toluene, highly
elastic at room temperature, and becomes brittle (in thin filaments)
under humid conditions. This reaction which differs from that of
alkyl-(aryl)-halide silanes with alkyl-(aryl)-ethoxy silanesp was
Card 1 ~5

86393
The Reaction of Heterofunctional Condensation S/020/60/135/002/018/036
of Bis-(trimethylsiloxy) Titanium Dichloride B016/BO52
With Phenyl-methyl Diethoxysilane
thoroughly studied. It is shown that not only phenyl-methyl diethoxy-
silane but also dimethyl butoxysilane reacts with bie-(trimethylailoxy)
titanium dichloride to form trimethyl silane chloride instead of butyl
chloride. The chemical composition of the resulting polymer indicates V~
that the reaction described here is very complicated. Further experi-
ments proved that the reaction is initiated by humid air reacting with
bis-(trimethylailoxy) titanium dichloride. Thus, HC1 is split off
(Scheme 11 *(1)). The initial reaction product reacts with phenyl-methyl
diethoxysilane while alcohol is separated. HCl reacts with the trimethyl
siloxane group bound to titanium under the formation of trimethyl silane
chloride (Scheme 11 (3)). Alcohol reacts with trimethyl silane chloride
to form small amounts of trimethyl ethoxysilane (Scheme 11 (4-6)). The
alcohol produced during the reaction reacts with HC1 to form trimethyl
silane chloride, trimethyl ethoxysilane, and the polymer. These reac-
tions were confirmed by further experiments in which bis-(trimethyl-
siloxy) titanium dichloride was converted into a polymer even in the
presence of small amounts of water (Scheme 111 (1-3)). There are
3 Soviet references.
Card 2/ 6

86393
The ReactioP of Heterofunctional Condensation S/o2o/6o/i35/002/018/036
of'Bis-(.trimethylsiloxy) Titani*um Dichloride B016/BO52
With Phenyl-methyl Diethoxysilane
ASSOCIATION,: Institut elementoorganicheskikh soyedineniy Akademii
nauk SSSR (Institute of Elemental-organic Compounds of
the Academy of Sciences USSR)
SUBMITTED: july 6, 196o
CHz
1. 2 Colis S1 (OCIH&), + 3r%l',*rl' 10SI (CHIJI
OCIH, CHs OCIH5 t
OSI (CH&)s CH~ vv
Scheme I
0- 1-0- S1-O-4v-O-51_U_ it- + 5 (CHS)SSIC1,
C Cl
I QHS OCIHA
Pard 3A

86039
Bo16 B054.
~ndri corresponding Member AS USSR, and
Synthesis of Diatomic'Alcohols of the Siloxan4 Series.
Synthesis-of Big(A-hydroxy-ethoxy-m'ei-hy-l~--p'olydimethy1
Siloxanes
OP
Doklady Akademii nauk SSSR, 1960, Vol. 135, No, 3,
pp. 595 - 598
TEXT: The a~uthor.s report on the synthesis of bivalent organosilicon
alcohole with hydroxyl groups in the organic radicals. They succeeded in
synthesizing such alcohols with 1, 2, 12, 13, 20, and 21 dimeth3(l siloxane
members, nameiy bia(A-hydroxy-ethoxy-methyl)-polydimethy1 siloxanes (BHPS)
withis. molecular weight of 360-180o. To produce such dimethyl-siloxane
olig mare with 3-hydroxy-ethoxy-methyl groups at the ends of the chain,
the luthors studied the cohydrolysis of dimethyl-diethoxy silane with a
heterocyclic derivative (the synthesis of the latter is described in the
authors' paper, Ref. 3) (reaction (I)).
Card ~1/5

86039
Synthesin of Diatomio Alcohole of the Siloxane S/020/60/135/003/023/039
Seii4s. Synthesia of Bis(A-hydroxy-ethoxy- B016/BO54
methyl,l)-polyaimethyi Siloxanes
(C~~3 EEHICHIRHI, _.PIIHTe3 _xoToporo 6un onticatt a npeAblAylgem COM- .1
n.o-peaKRIIIIJ
0 - cli,
1l'0
(CHs)..Sl (OC4H&)2 + 2 (Clis)ISI CH3
\Cli, - 0
CH cli CH,
t. LICH30CHCH%OH.
&I L13 4

66039
Synthesis of Diatomic Alcohols of the S
/020 60/i35/003/023/039
Siloxane Series. Synthesis of Bis(P-hydroxy- B016/BO54
ethoV-methyl)-polydimethyl Siloxanes
This reaction is based on the good hydrolyzability of the heterocyclic
derivative. The authors made the hydrolysis in aqueous-acid medium without,
a solvent. The reaction proceeded according to scheme (I); it was, however,
accompanied by a side reaction of the hydrolysis of dimethyl-diethoxy
silane with a fbrmation of octamethyl cyclotetrasiloxane (reaction (IM.
(CH3)2SI-O-Si(CHa)s
fl'o
4 (CH3)-Sj .1 13)g + 8c,11,01 1.
(CHI)2~1 - 0 - 11 P 13)2
Thus,, the quantitative ratio between the dimeihyl-diethoxy silane-used and
the heterocyclic derivative was modified, which led to tho formation of
BHPS with about half the number of dimethy! siloxane members as would
correspond to the ratio of the components used. Therefore, the authors
modified the conditions of hydrolysis to reduce the side reaction by
adding water according to the equations: A - n/(n-m) (Ref. 4),'where A is
the number of dimethyl siloxane members, n the number of moles of the
heterocyclic derivative, and m the mole number of water. Under these con-
Card 3/5

86039
Synthesis of Diatomic Alcohols of the Siloxane S/020/60/135/003/023/039
Series. Synthesis of Bia(A-hydroxy-ethoxy- B016 B054
methyl)-polydimethyl Siloxanes
ditions, BHPS are formed with a number of dimethyl siloxane members which
nesrly corresponds to the number given according to the reaction. Hence,.
the authors conclude that the reaction exclusively proceeds according to
scheme (I). The yield in BHPS attained 80%, And no polydimethyl siloxanes
were formed. For the synthesis of BHPS, theyalso used the reaction of
catalytic transformation of octamethyl eyoloietrasiloxane with H so it
2 4'
produces -linear'poly4imethyl siloxanes (scheme (III)).
(CHS)ISI-O-SI(CUS CHI CH CHI
!!'-S"- HOLOS LOS03H.
10
CHI
By an adjustment of the quantitative ratio between H so and octamethyl
2 4
cyolotetrasiloxanet the degree of polymerization can be varied within
-required limits. The second step of the reaction is based on a cohydrolysis
.of the oligomer produced according to scheme (III) with the heterocyclic
deirivative mentioned at the beginning. On the basis of their results, the
Card 4/5

ANDRI ; ASNOVIC111 Emmanuil Zinovlyevich;
PETRASHKO, Aleksey Ivanovich.; NMUWUDOVAt A.S., red.; SAVCHENKOp
Ye.V., tekhn. red.
[Chemistry of large molecules] Khimiia bol'shikh molekul. Moskva.,
Izd-vo "Znanies" 1961, 39 p. (Narodnyi universitot kulltury:
Estestvennonauchnyy fakul'tett no.18) (MIRA 15:1)
1. Chlen-korrespondent AN SSSR (for Andrianov).
(POLYMERS)

ANDRIANOV, Kustma Andrianovich. Prinimali uchastiye: PARKShEYAN, Kh.1t;
SEMENKOI P.Ya.; ZABYR1NA, K.I. , red.:
KALIMANSKlYsV.I. I red.; KORITSK17t Yu.V. . red,; avALiKovsm,
AN., red.; EPSIITEYN, L.A.., red.
[Macromolewilar compounds for electrical insulation) Vysoko-
molekuliarnye soedineniia dlia elektricheskoi izoliatsii. Mo-
skva, Gos. energ.izd-vo, 1961. 327 p. (Polimery v elektroizo-
liatsionnoi. tekhnike, no.1) (HIM 15:2)
(Electric insulators and insulation) (Polymers)

37753
.T. 31 oib 3/661/61/000/006/004/081
I/. I'a 510 D205/D302
AUTHORS; Trofimova, I. V.,-Andr-ianov-,-K. A., Golubtsov, S. A.,
Turetskaya, R. A., Belyakova, i-.-'V., YakuBheva, T. M.1
Lobu8evich, N. P. and Luzganova, M. A.
TITLE: On the regulation olf the composition of products in the
direct synthesis of,methyl- and ethyl chlorosilanes in
a fluidized bed
SOURCE: Khimiya i praktichebkoye primeneniye kremneorganiches-
kikh soyedineniy; *udy konferentsii. no. 6, Doklady,
diskusaii, resheniyb. II Vass. konfer. po khimii i prakt.
prim. kremneorg. Boyed., Len., 1958. Leningrad, Izd-vo
AN SSSR, 1961, 25-27
TEXT: Regulation of the proceSs is one of the main problems in
I
preparing monomeric organoailioon compounds. The most intensting
results were obtained during the Attempt to regulate the product
composition by varying the prejarition procedure of the catalyst.
Card 1/ 3

3775h
Yl 10 -0 S/66 61/000/006/005/081
la5b D205YI)302
AUTHORS: Lobusevich, N. P., Trofimova, 1. V., Andrianov, K. A.,
Golubtsov, S. A. and Belyy, A. P.
TITLE: Influence of some metal additives on the activity of
silicon-copper alloys in the synthesis of methyl chloro-
silanes
SOURCE: - Khimiya i prakticheskoye primeneniye kremneorganiches-
kikh soyedineniy; trudy konforentaii. no. 6, Doklady,
diskusaii, resheniye. II Vses. konfer. po khimii i
prakt. prim. kremneorg. soyed., Len., 1958. Leningrad.
Izd-vo AN SSSR. 1961, 28-31
TEXT; 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 chlorosilane synthesis was investiga-
ted. Two series of alloys were r ar ed-_l) From purified Si with
less than 0.2% of impurities; 2~ ferpom Kp ,I(Kr-1) silicon with 2%
impurities. These alloys, notwithstanding the identical procedure
Card 1/2

37759
S/661/61/000/006/016/081
D205/D302
AUTHORS: Popeleva, G. S.,.Trofimova, 1. V., Andrianov. K. A.
and Golubtsov, S. A.
TITLE: Study of,vinyl chlorosilane synthesis
SOURCE: Xhimiya i pralctielieskoye,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 3CH 2 = CH01 + Si
CH 2 =CHSiCl 3 it was found that the catalyst prepared from preci-
pitated CuO, Si powder and a liquid glass binder .-:as the most' ac-
tive. 3 methods of contacting were tried: (1) Stationary bed of
elletized catalyst (2 - 3 mm pellets); (2) an agitated powder,bed;
a fluidized bed. The first method gave good results when using_
M
anhydrous FeCl 3 as an activator. The second method allowed the low
Card 1/3

3/661/61/000/006/016/091
Study of vinyl D205/D302
ering of the temperature from 460 to 4200C. The vin 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 -26~. In contrast to the synthesis of
methyl, ethyl and phenyl chlorosilanes where the best results are
obtained in the fluidized bed,, this method does not provide the
contact times necessary for sMnthesis of vinyl chlorosilanes. As an
alternative to,*the above reaclion, the reaction HSiCl 3 + CH2
CHSiC1 + HC1 is proposed. This reaction was investigated, yields
3
of 654, being q~tained at 50006 with a contact time of 35 seconds,
0
In the synthegis of methyl vinyl dichlorosilane by the reaction
CH3 SiHcl2 + CH2 = CHC1--,~CH3(CH2=CH)SiCl2 + HClj the optimum con-
ditions ensuring a 555', yibld wore 54000 and a c'ontact time of 30
seconds. Thus the condensation of hydrochlorosilanes with vinyl
Card 2/3

oqo 0 V
S/66 61/000/006/019/081
D205YD302
Go-
AUTHORS: Tarasova, A. So, Petrov, A. Do, 1~
lubtsov, So No, Ponomarenko, V. A., Cherkayev, V. Go,
J
Zadorozhnyy, No A. and Vavilov, V. V.
TITLE: Continuous addition of hydrochlorosilanes to unsatura-
ted compounds
SOMICE: Xhimiya i prakticheskoye primeneniye kremneorganiches-
kikh soyedineniye; trudy konferentsii, no. 6, Doklady,
diskussii resheniye. II Vses. Konfer. po khimii i prakt.
prim. kremneorg. Soyed., Len. 1958. Leningrad, Izd-vo
AN SSSR. 1961, 91)-100
TEXT: Por practical application of the addition reactions of me-
thyl diolilorosilane, 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

Continuous addition of ...
S/661/'61/000/006/019/081
D205/D302
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-
chlorosilane. The experiments havo shown that in tho 35 - 2000C
temperaturd range the reaction is unchanged giving a 65 - 7%
yield. No by-products are formed and the output is hi5h (,> 6 kg
of nothyl othyl dichlorosilane/hr/l of reactor volume . The pro-
cess is amdnqble to automation owing to its insensitivity to tem-
perature changes. There are 1 figure and 1 table.

Card 2/2

S/66 61/000/0005/0306/031
D202XD302
."t"MORS: Alashkevich, 1-1. L., Leznov, N. S., Yumakova, A. Ye. and
Arldr.-anov, K. A.
TITLE: Ph,-sico-Mechanical properties of lilnear polydiethylsi-
lox'Ines
jr
SOUIRCE: J~juniya i prak-ticheakoye prineneniye kremneorganicliskil 'h
soyedineniy; trudy konferentsii. no. 06: Doklady, diskus-
sii, resheniye. II Vses. konfer. po khimii i -orakt. prim.
kremneorg. soyed., Len., 1958. Leningrad, Izd-vo UN SSSR,
1961, 171-172
TE'XT: A supplement to a previous report in no. 2, p. 20, of this
Publication. The authors compare the properties of polymethyl-phe-
nylTsiloxanes with those of polydiethyl-siloxanes used as high-va-
cuum pump fluids. No experimental details are given. It was found
that the first compounds have marked advantages over the second,
although cyclic polymers, formed during -'%-.heir synthesis, unfavorab-
ly affoect the thermal stability of both.
Card 1/1

.2/6 6 /61/000/006/0-.-0 8/061
D202IV302
iWTHORS: ICuznetsova, A. G., Andrianov, X. A. and Zhinkin, D. Ya.
TITLE: On the co-hydrolysis of diethy1dichIlorosilane and )hcnyl-
trichlorosilane
so" n., CE: Khimiya i prairticheskoye primeneniye I:re:-:ncorGZLniCYIcSkikh
soyedineniy; trudy kon-ferentsii. no. 6: Dohiakiy, diskus-
sii, resheniye. II Vsea. konfer. po 'Ac-himi I prukt. Prim.
kremneorg, soyed., Len., 1958. Lenin6rad, Izd-vo AN S33RI
1961, 175-179
T"EXT: A discussion on a previous report (no. 2, P. 33, this Publi-
cation) ir. which the authors and P. V. Davydov (Hoscow), N. 3. Lcz-
.Iov (Moscow), N. N. Sokolov (VEI, Moscow) and A. V. 1"'arlin (VIIIISK,
L
' solvents, especially t), f
Le*ningrad) took part. The role o a , o
ethyl-ether, in the co-hydrolysis process of the above-mentioned
compounds and the unfavorable effect of methyl-tric11orosil.-ne ad-
mixtures in dimethyldichlorosilane used in the process verc diu-
cussed.
Card 1/1

L6 30".104 0/081
0 2 / D-1-1- 0 2
AUTHORS; D:; h e 1, c I ~. e 1 ' S, -, i I YA17 0 V 31,11' 0
Yu. K.
T I T L""z' The catalytic
SOURCE: Xhimiya i pral:ticheskoye primeneniye kremneorganichies-
~6 1. ',"h uoyedineniy; t-rudy konferen.-isii. no. 06: Dolklady,
diskussii, resheniye. II Vses. konfer. po ',,himii i prakt.
prin. kromneorg. soyed., Len., 1958. Lenin-rad, Izd-vo
'uq 53SR, 1961,
TEXT: A discussion on a previous report (no. 2, p. 451 this b-
lication) between K. A. Andrianov, N. N. Sokolov ~VEI, moscow , A*
V. Karlin (VNIISK, Leningrad) and M. 0. Voronkov tMiS AS USSR).
The catalytic effect of NaOh on its thermal stability lat 30000), as
well as the possible use of quaternary anmonium bases as catalysts
and the inef1piciency of acidic catalysts were discussed.
ASSOCIATION: Vsesoyuznyy elektrotelchnicheskiy institut im. V.I. Le-
nina, Moskva, (All-Union Electrotechnical Institute im.
Card 1/1 V. I. Lenin, M oscow)

3?765
573100
6/66 1 A I /UOO/jjO"/J-'TV081
D244/D302
;-.U T' I i 0IMdrianov, K. A.
T !TLE On the more important trends in zh-c- d-cveloj:~C-.,-z of orz.-a-
nosilicon compounds
S O'd R CE,' Khimiya i prah,ticheskoye primeneniye
kikh soyedineniy; trudy konferentsii; no. 0"; Doi:izdyl
diskussii, reshen-iye. II Vses. konfer. po J':hiimii i 'prajk.t.
prim. 'Kremneorg. soyed., Len. 1958. Lenin.-rad, I-,,d-vo
AN SSSR, 1961, 213-216
T*EXT: This is a discussion in which N. F. Orlov (Da.3 Sj..~33R, Lc-
ningrad), Ye. PI. Opurina (IMoscow), V. I. Palkhomov (IIIIPI-11 :-'O~;cow) ,
0 -
S. In. 3orisov (VNIIDK, Leningrad) ' A. I. Dintses (I'OSCO%-.'~z, nd P. P.
Nikotin ("Sevkabel" Plant, Leningrad) took part. The W.t"101' kl.:3-
closed that the work on the synthesis of poly:rers %iit'-I O'i-O-Al lin."s
is directed toward preparing rigid and elastic polynor., II'---w
polymers do not liquefy at 500 - 6000C, and dissolve in, benzene,
k,oluene and certain other solvents. They are 6ood hardenern
Card 1/2

n 24
0
the more imDortant ...
f o r t,- -e silicon organic resins. The pl:-,s-.-ic 6-as~;e~; ca:~
moul ed by usual methods, and can withstand %%rorl-inc- Of
d
400 - 4200C. In addition, poly o rguno-al tzm'Moo i I ox,,-,- of iri'uc-
rest from the point of view of the study of lntro,!~,ctiun
of A! into siloxane structure gives soluble molrculeos, the otruc-
Uure o.L which is akin to that of silicates. The molecul---.r Is
about 40,000. Preliminary work indicated thaz inciuzcion of cQrtotin
solvents into the polymers gives optically trzarsparent n4ateria".3
re-~aining the properties of rigid polymers. Tre
such, systems is their hi -h brittleness. Inves 4.i -a'L4 on of n,)1y:-.crs
containin.m Ti indicated that the bond Si-O-Ti i~; very ot~tbie to
hydrolysis. Only 3.5% of the titanos-iloxane polymer hyd.rolysed
with 20 - 30" HC1 for 10 hours, whilst kaolin is completely hydro
lyzed under these conditions after 3 - 4 hours. Practic----l utilizati-
on of the titanium polymers is difficult because of inoi.-abilily of
lihe Ti-C bond. It iL3, therefore, necessary to have C-O-Ti links.
C--rd 2/2

S/661/61/000/006/05 0/081
D235/D302
AUTHORS: iozlovskaya, L. N., Glukhova, A. I., Andrianov, K. A.
and Kalu,liheninag X. F.
TITLE: Thermal stability of materials based on poly-dimethyl-
siloxanes
SOURCE: Xhimiya i prakticheskoye primeneniye kremneorganiches-
kikh soyedineniy; trudy konferentsii, no. 6:Dolrziady,
diskusaii, resheniye. II Vses. konfer. po khimii i
prakt. prim. kreTineorg. soyed., Len. 1958. Leningrad,
Izd-vo AN SSSR$ 1961, 216-220
TEXT: A supplement to the above paper (this publication, no. 2,
P. 95). The authors report on materials formed from polydimethyl-
siloxanes and fluoro-organic polymers. Such materials can be used
at 3500C for 300 hours and at 3000C there is practically no change
in the properties after 1,000 hours. After service at 300 - 3500C
the mechanical strength is 100 - 110 k9/cm2 and the specific elon-
Card V3

S/661/61/000/006/050/081
Thermal stability of D235/D302~
gation 80 - 100%, the resistance to breakdown after the action of
oil for 200 hours at 2000C falls by 40 - 50% and swelling amounts
to 20 - 25%; shrinkage after heat treatment is about 55. The ma-
terial can be used for packing, sealingp etc.; because it forms
few volatile compounds it will find application in vacuum technolo-
'. T' aper is discussed by the authors and A. L. Klebanskiy
GlInSKe,pLeningrad), A. A. Berlin (Moscow), V. I. Pakhomov (NIIPII,
F
Moscow) and N. Nudellman (NIIRP, Moscow). The following topics are
discussed: Vulcanization of the polymers; toxicity of the material;
the immediate formation at room temperature of polymer fragments
on rolling; properties; the mechanism for the formation of polymer
fra.g.1rilents by destruction of Teflon and polydimethylsiloxane; and
the amount of filler for the material. Vulcanization talkes place
by breakdown of polymer chains, the formation of benzoyl peroxide
and subsequent recombination of the macromolecules; it takes place
with respect to fragments of polydimethylsiloxane and not with res'-
peat to the fluoro-polymer. The number of volatile compounds is .
negligible and the material does not cause metallic corrosion. The
Card 2/3

S/661/61/000/006,/051/081
D235/D3O2
Aur,Niolls Zhdanov, A. A. and Andrianov, X. A.
T-TLE: Polyorgano-metallo-siloxanes and p olyorGano-siloxy-mc-
talloxanes
SOURCE: Khimiy i pra'il-.ticheskoye primeneni'ye
kikh soyedineniy; trudy konferentsii, no. 6: Doklady,
diskussii, resheniye. II Vses. konfer. po
prakt. prim. kremneorg. soyed., Len. 1958. Lenj-n'-;rad,
Izd-vo AN SSSR, 19619 220-224
TEXT: A discussion of the above paper (this publication, no. 2,
p. 100) between the authors and N. P. Orlov (IKhS AN 33SR, LQnin-
,:-rad), S. N. Borisov, (VNIISK, Leningrad) and 1-1. G. Voronkov (IKhS
AN SSSR, Leningrad). The following points are dJLsc.,oscd:
and hydrolytic stability of the bonds silicon-oxygen-nesal;
duction of the elements magnesium and zinc into ihe ziloxane Struc-
ture; the formation of poly-diethyl-alumi-na-siloxane; reasons -for V/
the increase in thermal stability obtained by the au-t~'-iors; zhuri-xal
Card 1/3

S/066' 1/6 1 /000/0015/051/031
Polyorgano-metallo-siloxanes ... D235/D~02
and hydrolytic stability of poly-organo-titaniu-m siloxanes. The
thermal stability of the bonds Si-.0-IM is fairly hi-h and ., compound
such as (R SiO )Ti is hydrolized only very Slowly by wit-~er. Na.r.-e-
sium reactl lifte aluminum with hydroxyl containing silicon c'unopounds
U
to give hydrogen and the siloxane polymer containingmaL;n o s i um . R c -
ference is made to a patent by Viberg and Katnslev %-.rhere poly-d-i-
ethyl-alumina-siloxane is obtained by reacting-the metal with di-
ethyl siloxane at 310OC; the authors only obtained a 1.5 - 2~'j yield
by such a reaction. Alkaline hydrolysis of dime '%Kyl-siloxane with
aluminum chloride in the ratio Si-Al of 3:1 t 0 45:1 leads to the
formation of gel-like polymers and in the ratio 3i;'1 of 60:1 to
100:1 -too co-polymers similar to poly-dinethyl-siloxane rubbers,
but the exterior is frequently gummy. Thermal mutability of pDly-
organo-titanium-siloxanes is considerably higher t'''an for !he lalu-
minum compounds. The bond Si-O-Ti has hi6her thormal i~tability than
the comoounds with a siloxane bond due to the offect of oxygen on
Si-C under the actibn of titaniun. The hydrolytic otabilitY depends
on ihe nature of the radical connected to silicon and the molecular
structure. Derivatives from elements of group V possess the greatest
Card 2/3

3/661/6 1 /00J/0061/05 1/031
Polyorga:io-metallo-ailoxanes D235/D302
stabJ li ty, as compared with derivatives from group3 III and IV, but
there is no qua,,-Ititative information concernin6 this.
ASSOCIATION: Institut elementoorganiches' hadenii
Kikh soedineniy A
nauk SSSR, Moskva (Inatitute of Elemental Organic
Compounds, Academy of Sciences, USSSR, Moscow)
Card 3/3

3900
37766
S
/661 61/00'0/006/052/051
00 /
D235/D302
AUTHORS: 1-1-indlin, Ya. L., Lcznov, N. S. and Andrianov, K. A.
TITLE: Synthesis of polymethyl-siloxanes w4th hy,;ro%y, :"-ou,)s
in the o,-ganic radical u-
SOURGE: Xhimiya i prakticheskoye primeneniye
soyedineniy; trudykonferentsii, no. 6: Doklady, dio'k.us-
sii, resheniye. II Vses. konfer. po 1thim-ii -i praz,:t. prim.
kremneorv. soyed., Len. 1958. Leningrad, Izd-vo Sj3R,
1961, 224-226
T'--'XT: A supplement to the above paper (this pub-ication, no. 2,
p. 127). r,,".,-.,e authors report on the exceptional antifoam properties
of poly-methyl-siloxanes with a hydroxyl grouj in the or-unic r:.di-
cal. Such a compound depresses foam formation dur-in.- fox-;%entation
o f anumber of antibiotics and the exDenditure of the a-ent
is only a hundredth or thousandth part of a percent of thle colum-c
of the fermentation medium. Such an antifoam agent, containing; 5~,`4
nydroxyl groups in the form of a 10 - 15~o solution in white soirit
Card 1/2

1D
37775
S/661/61/000/006/068/081
D247/D302
AUTHORS: Konstantinova, N. G., Zhdanov, A. A., Andrianov, K. A
Aarov, 11. Ya. , Kyutner, D1. A. and Z~WTa_rov,
TITLE: Thermostable lacquer coatings based on silico-organic
polymers
SOURCr":' Khimiya i prakticheskoye primeneniye kremneorganiches-
kikh soyedineniy; trudy konferentsii, no. 6: Doklady,
diskussii, resheniye. II Vaes. konfer. po khimii i
prakt. prim. kremneorg. Boyed., Len. 1958. Leningrad,
Izd-vo -AN SSSR, 1961, 296-299
TEXT: A study was made of the thermostability of several lacquer-
painted materials on the basis of different film-forming substan-
ces. The BiliCo-organic resin K-47 was modified by the use of orga-
nic polymers to give a hard, cold-drying coat of increased thermo-
stability. The metallic surface and its preparation was found-to
have a great influence on thq adhesion, the protective properties
and the thermostability of the coatings. In the discussion, the
Card 1/2

3/66 61/000/006/069/081
D247XD302
4'%'U T11 10 R SFromberg, M. B., Andrianov, K. A. and Zabyrina, K. I.
TITLE': Block polymers from polyorganic silicones for electrical
insulating coatings for air drying
SOUROE: Khimiya i prakticheskoye primeneniye kremneorganiches-
kikh soyedineniy; trudy konferentsii, no. 6: Doklady,
diskuseii, resheniye. II Vaes. konfer. po khimii i
prakt. prim. kremneorg. soyed., Len. 1958. Leningrad,
Izd-vo AN SSSR, 1961, 299-300
TEXT: The text is in the form of a discussion in which A. F. Moi-
seyev (Moscow) took part. Some thermal and mechanical properties
of the polymers (thermostable up to 20000) are mentionedo and in-
direct evidence for their block structure is given.
ASSOCIATION: Vaesoyuznyy elektrotekhnicheakiy institut im. V. 1.
Lenina, Moskva (All-Union Electrotechnical Institute
im. V. I. Lenin, Moscow)
Card 1/1

S/1,10/61/000/001/001/023
E194/E455
AUTHORS: 0v K Corresponding Member AS
GolubeTtko. N1,A., Engineer
T TTL F Cast Insulation Based on Fpoxide Ri-ins and
Polyorganosiloxnnes
I1'PRTODTCAJ- Vestnik elektrol)romyshlennosti, 1961, No.l~ pp,J-1
TNXT: This article describes cast insulation which has been
dt~velOpod on the bastq of epoxide resins and polyorganosiloxanes.
Polyorganosiloxanes have good electrical and thermal Wit poor
mechanical properties; they can, however, be combined with certain
orgranic polymers to form block polymers In Ilie caso of poly-
organosi.loxanes the reactive ITT-oups are hydro-xvi-A and osters and
in the epoxide reqins thov are epoxide and hydrox".1 gri-ollps.
Epoxide resin grade 3-37 (P-17) wa-; self-cled a-4; bi-aj~; ht-c'11jR(-
besides haviny gnod ca!pting properti.os i t lia -4 aJong hardeningr
time, Polvorganosiloxtitte.-4 of* vartoiis compo-;xt ions. and ~,trurtilres
mw-ty be dc-rived from sili,~on-nrgrani-: monontr.--~;a utethvl nhrnvi-
(lichlorsi)anp and dimethvIdichlorsi lane I'lie ~-ontent oF hvdr(ix%,l
~rrollps iii the polvor~rnii(isiloxanv- i,; I to V~i- otift of' (,ihci-.%,Vl "Troull.;
fro"i t to ON. The opoxidr. i-f-4in4 aro -ombitiod with polvorgann-
Card JA

88640
S /I I o/6 i /f)(101/v(I I /()() I
F r)4/r4ii
Cast 7nstilation Ila sod on Epfix ide Re-xi ris nw I Ilo I yorgatit is I I oxanes
siloxnnes either In a solvent or in the r1wid conditicin and tlif,
result.i_ng compounds contain 0-om 10 to %M)'Y~ of po1y(Nrznnosi)o-,;11ior-
The resititing compounds are utifftirm t.rntisn;)rPn1 prodticts rtinging in
colour from light vell.ow to dark by-niin, The becniiie
liquid at 111) to IOOOC and can be mnintninvd at thi-A tempei,a tilre Cor
a considerab)e tAme withotit chnnge. Thell llinthod of, use ip '.4jillple
"tilt
-4imilar to that of Ppoxide. compnim(k. M'Iterl"118 that call he
iised as bai-de-ners for 9K IEK ) nompoiirid.-% lvo plithalvic or twileir.
anhydrides , amines , polya lumino-oricano-; i loxanes and ot tiers . Tbe
quantity of hardener depends .,nn the rontent of epoxide grniip.,1 in
tile. compound and usually ranges from 5 to 201-4 by weight. Thv
c,impounds are hardened at a temperature of 1411) to 200'r. which
U!,nn'lly takes several hours. Then the ca,~t compounds are hoat-
treated at 150 to 200"C for 24 to 48 hotirs. ,This beat treatmont
improves the dielectric properties. The jifiv-iical propertipq of
thf, compounds ctepvnd (in the content and ;;trnctiire of the-
poJyorganosiloxanes, Mineral fillers may be used. The greater
the content of pol.yorganosiloxanes the greater the plasti-elt.y.
Shritikagi, or PH compounds containing 20 to 30% of polyorgajio-
Card 2/11

5Z.11 1 10 ),/(1() 1 /023
V 19 if / 1, 14 15
Cast fii-oilation Based On Fpc)xldf-. PPAITIs Mid PislVorgill)(s.4i IOX0111-A
five days tit water, Tho d ie I ec t. r j c pvtstl-, t i f- ma j it I y dopend on
tho.,q(. tit' the epoxide remin gradt, F-17 nscd in pt-paritig the
compolinds , There was littAp increaso in dit-loctric lwts with
Voltage tip to '35 Mr~ Compound FK..20 wilb tpiart.7 uand A4 l'illor
had a tiower ractor of 0~011 (it 20'C atid 0,0V at IVI .C - A I't v r
agreing at 200IT for 600 hoimq tfie 1'.~rior at 20 *(' rose from
0.0023 to 0.0012. A tropical huntidity tp!~t ot' more than 900 hmirR
has practically no effect on thv rivolit.-T-1 ie~. Cnalprilind
EK-20 has been. used for imprognatingr and "ptilt ing" non-rotating
components operating at vimg:itigr frrsm -(),) to ~20WC,
There are 2 figitres. 5 tables and It rt-ferencoc: ~,zov)vt and
I non-SoAriet.
SUBMITTED. march 11 , 196o
Card 4/4

69939
S/191/61/000/002/007/012
Comparative properties of organo... B124/B204
in air was compared. Fig. 1 shows the dependence of the viscosity of the
compounds I and II upon the heating time at 2500C. Fig. 2 shows the changf
in viscosity of the compounds III and IV with the heating time at 2000C.
Fig. 1 shows that the viscosity in the case of heating at 2500C grows more
quickly with compound I than with compound II. The results obtained by
the analysis of the chemical composition of the liquids investigated
(Table) show that in the case of heating, the molecular weight and the
silicon content in compounds with a methyl siloxane chain (I and III)
increase more quickly than in compounds with the siloxane chain (II and IV
which characterizes the destruction processes in the organic part of the
molecule. The organomethyl siloxanes (I and III) are also less resistant
to thermooxidation. The substitution of the oxygen of the methylene group
in the molecule chain of organosiloxane weakens the shielding effect of
the siloxane bond in comparison to the silicon-organic fram groups, which
leads to a decrease of thermooxidation stability of the frame groups. The
temperature coefficient of viscosity grows in the interval of from +50 to
-300C considerably in the case of substitution of'oxygen in the siloxane
Card 2/~v

S091,9
Comparative properties of organo...
5/191/61/000/002/007/012
B124/3204
chain by the group -C.H2-; in compound I it equals 330 and in compound II
35 (Fig- 3). Compounds III shovis the same temperature dependence of
viscosity. The absolute value of the viscosity coefficient in the tempera-
ture interval of from +50 to -500C is, however, considerably lower, in
compound III it amounts to 12.9 and in compound IV to 7.65 (FiG- 4). As
initial compounds, chlorosilane, dimethylehloro.-nethylcl-lorosilane, di-
methy1dichlorosilane and methylphenyldichlorosilane were taken. The
compound with a methylenesiloxane chain is obtained by means of the
reactions:
"to
sic, + (0ioxvisia
(CHJ3S1-O-S1(CH~..C14,C1 -L 2HCI
IV
(C'12)jS'OS'(C".')'Cj1'C1+A1g ._P_ (C%)JS!OSi(CF13)jCHjA1gC1
(CHj3S(OSj(cH,),C1i..mL'C),+ (CH.')..SjCj'
(CIVAOSI(CH~,-CH,-sl(CH~,C1 +j%jgCj,
Card 3/y V11.
A
14Z
IN
t
14

69919
Comparative properties of organo...
3/191/61/000/002/007/012
B124/B204
kfagnesixim-organic compound VI is not only formed in sulfuric ether but
also in toluene, howeverg the reaction to the co'-
mDounds VII and VIIIin
toluene, does not develop quantitatively in toluene also if the reaction
time of 8 (in ether) is extended to 13 hr in the reaction rith dinathyl-
dichlorosilane and to 30 hr in the reaction with methylphenyldichloro-
silane. There are 4 -figures, I table, and 3 non-Soviet-bloo references.
Legend to Fig. 1: Change in
viscosity in heating up to
250OC; 1 - compound 1;
2 - compound II; a) viscosity,
centistokes; b) heating time, hr.
L
Card 41,01
-),SIOSI(avICH%SjPV*CI + HSO ~
2
(cli. CH,Sjp~1110 + 2HCI
ItCH~'SIOSI(PN
(CIV3S1-0-SI(CHS)'al'~igC~+ Cli'C"SICI'
, (CH~,Si-O-SI(CH~2CH,SiCti,CH,,CI + Mgcl,
Vill
2(CH,),Sl-o-sl(cti~sciiss'CHACGHICI + HSO
I(CH~,S,_O_S,(CH~,Cli.SiCti.,CH,1,02HCI

.2.0939
220CL IM S/062/61/000/003/005/013
ob B117/B208
AUTBORS: Andrianov K. A-and Nikitenkov, V. Yo.
TITLEs Synthesis.of organosilicon compounds with phenylene
siloxane.ohains,of the.mbleoules
PERIODICAL: Izvestiya Akademii nauk SSSR. Otdeleniye khimioheskikh
~naukj no. 3, 1961, 441-444
TEXTs The authors studied. the hydrolysis of 1-methyl-phenyl chloro silane-
4-phenyl dichloro silane benzene-and 1,4rbis!--(pheny1 dichloro silane
benzene in an aqueous ether medium. HydrOlyBiS of 1-methyl-phenyl chloro
silane-4-phenyl diohloro silane benzene takes place in an acid medium to
form a crystalline compound in a yield of 99.1 % according to the soheme.t
Card 1/6

20939
S/062/61/000/003/005/013
Synthesis of organosilicon... B117/B208
OH
CHS CI CHi.
~,- (CH ) Si OSi__ Cl
3)2S'014 3 3 3 3 1
CH 3-4n
Pure telomers with n = 29 3, and 4 were obtained from the reaction mixture
by fractional distillation. The phy9ioal-constants of the telomers are
listed in Table 1. The physical properties exhibit no anomalies. Tests
carried out with various molar ratios of octamethyl cyclotetrasiloxane to
trimethyl-chloro silane showed that at ratios of 1 : 1, 2 : 1, and 3 : 1
mixtures of telomers only, and no pure compounds were formed. In all of
these mixtures the telomer formed in maximum quantity did not correspond
to the stoichiometric ratio of the reactants. The telomer having a chain
by 4 dimethyl-siloxane units longer than would correspond to the
Card 2/4

1!;,. 8 110
27491
B/062/61/000/009/006/014
3117/B101
AUTHORS: Andrianov, K. A.p Zhdanovq A* A,,, and Odinets, V. A.
TITLE: Synthesis of liquid l,n-hexamethyl-poly(phenyl-ethyl)-methyl
siloxanes and investigation of their properties
PERIODICAL: Akademiya ne.uk SSSR. Izvestiya. Otdeleniye khimioheskikh
nauk, no. 9, 1961 , 1615-1624
TEXT: The lowest-molecular members of the polymerhomologous series of
l,n-h'examethyl-poly(phenyl-ethyl)-methyI siloxanea were synthesized and
their properties studied. The work was undertaken to study the dependence
of the polar properties of these liquid organo-silicon polymers on various
polar substituents at the benzene ring. The polar properties were
studied on the basis of the activation energy of viscous flow and the
temperature dependence of the viscosity. The flowing initial substances
were used for the synthesis; 0- (phenyl-ethyl)-methyl-dichloro silane
(C6H5C2H4(CH 3)SiC12, b.p. 90 920C (5 mm Eg)), (tolyl-ethyl)-methyl-di-
chloro silane (CH3C6H 4C2H4(CH 3)sicl2, b.pe 1030-1050C (2 mm Hg), (chloro-
Card 1/6

27491
8/062/61/000/009/006/014
Synthesis of liquid l,n-hexamethyl- B117/B101
phenyl-ethyl)-methyl-dichloro ailane (ClC6 H4C2 H4(CH3)SiC129 b.p..
1240-1-260C (2 mm. Hg). The synthesis d these Uompoundh is described in
Ref, 11 (Ko'A6 Andrianovp et al. Zh. obahch. 4imii (in print)). The
liquid polymers were obtained by the joint hydrolysis of toluene solution
of mixtures of these compounds with trimethyl-ohloro silane (b.p. 580-5900
at 90-950C- Polymers of varying degrees of polymerization, according to
the reactant ratio, may be isolated from the reaction mixture (Table 1).
Hydrolysis of ethereal solution of (phenyl)-mothyl-dichloro silane yielded
cyclic polymers also: tri(phenyl-ethyl)-trimethyl cyclotrisiloxane
[C6H5C2H 4(CH 3)S'013 and tetra(phenyl-ethyl)-tetramethyl cyclotetrasiloxane
IC6 H5C2 H4(CH3)Si 014' Evaluation of the infrared spectra of the compounds
investigated indicates that the addition of the vinyl aromatic nucleus
takes place in P position, giving P-substituted derivatives. The density
of the liquids was determined pyonometrically. Viscosity measurements
were carried out by standard methods with an Ostwald-Pinkevich
viscosimeter. Data on the activation energy of viscous flow and the
temperature coefficients of the viscosity are shown in Table 2. It was
found that for the lowest-molecular members of the homologous series the
Card 2/6

27491
8/062/61/000/009/006/014
Synthesis of liquid l,n-hexamethyl- B117/B101
activation energy of viscous flow is hardly dependent on the polar groups.
Substitution. of the hydrogen atom at the nucleus by methyl or chlorine,
however, always increases the activation energy. The activation energy of
flow-depends on the number of silicon atoms in the polymers under study.
The polar properties of the radicals investigated decreases in the order
-C H C H Cl > -C H C H CH > -C H C H There are 12 figures, 2 tables,
2 4 6 4 2 4 6 4 3 2 4 6 5*
and 12 references: 7 Soviet and 5 non-Soviet. The three references to
Engliah-language publications read as follows: C. C. Currie, Industr. and
Engng. Chem. 46j 2331 (19501 L. H. Sommer, R. P. Pioch, J. Amer. Chem.
Soo. J5, 6331--(1953)1 L. H. Sommer, W. D. English, G. R. Ansul, D. N.
Vivona, J.. Amer. Chem. Soc. 77, 2485'(1955)-
ASSOCIATION: Institut elementoorganicheskikh soyedineniy Akademii nauk
SSSR (Institute of Elemental Organic Compounds of the
Academy of Sciences USSR)
SUBMITTED: December 12, 1960
Card 3/6

27492-
s/o62/61/000/009/007/014
Reactions of bis(trimethyl- B110101
products Evidently the reaction
B Ci 3)3 Si 012 Biel2+ HCI ---> (CH 3)38"0 8'C12 +(CH 3)3 Biel (2)
H
takes place. The trimethyl-chloro silane formed thereby is then
transformed to a trimethyl-alkoxy silane,by the excess alcohol present.
This reaction, which was previously obse.rved with trimethyl-siloxy groups
bound to titanium (Ref. 1: K.,A. Andrianov, N. A. Kurasheva, Dokl. AN
SSSR 12,~, 316 (1960)) thus also occurs in the case of trimethyl-alkoxy
groups bound to silicon. The presence of traces of moisture is of great
importance for reaction (2). This is formed in the reaction
ROH + HCl;=:tRCl + H20. Since phenols do not react in this manner, the
reaction of bia(trimethyl-ailoxy)-dichloro silane with phenol leads to bis-
(trimethyl-ailoxy)-diphonoxy silane. The yield is 60-5%. To suppress the
side-reaction caused by hydrogen chloride, methods were used in the
experiments which either neutralize the hydrogen chloride or exclude its
formation. Bis-(trimethyl-ailoxy)-diethoxy silans was obtained in 68%
yield by etherification of bia(trimethyl-ailoxy)-diohloro silane with
anhydrous ethyl alcohol in the presence of pyridine. Various bis(tri-
methyl-ailoxy)-dialkoxy silane derivatives were prepared by treating
Card 2/4

27492
S/062j61/OOO/OO9/OO7/O14
Reactions of bia(trimethyl- B117/BlOl
in air and is easily soluble in toluene. There are 2 tables and 3 refer-
ences: 2 Soviet and 1 non-Soviet. The reference to the English-language
publication reads as follows: R. 0. Sauer, J. Amer. Chem. Soc. 66, 1707
(1944)-
ASSOCIA12ION: Institut alemenioorganicheskikh soyedineniy Akademii nauk
SSSR (institute of Elemental Organic Con.pounds of the
Academy of Sciences USSR)
SUMIITTED; February 2f 1961
Legend to Table 1.
Ill Formula, 01 q_P"Y_ T. KUM. d,
2 b.p.0 oc, 0 -_ -
3 calculated, [(C1i')'SiOhS1(O1C4H1-n)2 2U-234 C.4003 0.8847 90.94 96,01
4 found. 1(CHASiO),S1(0r_,H,-1), 225-227 1,3968 0,8757 96,94 96,88
jCH3)3Si0JS1(0CHj-n),
-1(C1-13)"Si0j'S1(OCjt1".0,
j(CHx)jS10).S1(OC2H&),'
j(CH3)3S10j,S1(0CH1),
((C1i')'S10J'S1(0C'"')'
Card 4/4
M-126 1,3943 0,8903 87,68 87,25
202-203 1,3875 0.8752' -67VG8 87,3i'~
M-193 1,3870 0,8921, - 78,~B 78'~10
174-175 11.1M5 0,9f55 69,16 68,84
15j-459 (3 mm)j 1.4.750 1 1,0330 1 100,59 100,85

28271 B/062/61/000/010/006/018
'b B1 17/B101
AUTHORSs Andrianov, K. A., and Severnyy, V. V.
TITLEi Telomerization of dimethyl cyclosiloxanes. Communication 3.
Telomerization by methyl vinyl dichloro silane and methyl
phenyl dichloro silane
PERIODICALt Akademiya nauk SSSR. IzveBtiya. Otdeleniye khimicheskikh
nauk, no. 10, 1961, 1788 - 1791
TEXTs Telomerization of octamethyl cyclotetrasiloxane by methyl vinyl
dichloro silane and methyl phenyl dichloro silane is described. The aim
of this paper was to investigate the effect of various substituents on
the course of reaction. In the experiments, octamethyl cyclotetra9iloxane
with boiling point 1740 - 1760c, methyl vinyl dichloro silane with boiling
point 930C (Cl 50.6~), and methyl phenyl dichloro Bilane with boiling
point 2000 - 2020C (C1 3746) were used. From the reaction of equi-
molecular quantities of octamethyl cyclotetrasiloxane and methyl vinyl
dichloro silane, a mixture of telomer homoloes was formed. From this
mixture, a-chloro methyl vinyl siloxy- W-chloro dimethyl ailoxanee with
Card 1/4 A

nla'
28271 S/062/61/000/010/006/018
Telomerization of dimethyl ... B117/B101
n - 1, 2, and 3 were isolated and identified on the basis of boiling tem-
perature, refractive indices, specific gravities, molecular refractions,
results of elementary analysis, and bromine numbers. The properties of
the compounds obtained are listed in Table 1. The mean conversion of
vinyl methyl diohloro silane was 32.8~, and that of octamethyl cyclotetra-
siloxane 54.0%. The yield of telomers was 45.1% by weight of the initial
mixture. Contents of the individual telomer homologs with n - 1, 2, and
3 were 18-5, 30.8, and 14.16~a, respectively. Higher telomers with a
polymerization degree n.-%3 were formed in the amount of 36.11~. Thus, it
was established that telomerization is the only reaction at the moment by
which compounds of the a-chloro methyl vinyl siloxy-6>-chloro dimethyl
siloxane series with given atomic number may be obtained. The reaction
of ootamethyl cyclotetrasiloxane with methyl phenyl dichloro silane
showed low conversion under standard conditions (3 hr, 2500C). Also the
experiments with 2 M methyl phenyl dichloro silane and 1 M octamethyl
cyclotetrasiloxane resulted in a total conversion of only 18.0' at 3000C
in 5 hr. The conversion of methyl phanyl dichloro silane was 9-1~, and
that of octamethyl cyclotetrasiloxane 19.0%. From the reaction products,
telomer homologs with n - 1 and 2 were isolated. 49.0% of the telomers
Card 2/4

Telomerization of dimethyl ...
f.L S/062/61/000/oio/OO6/018
B117 B101
had a boiling point higher than 3500C (3 mm). The properties' of the
resultant a-chloro phenyl-o-chloro nongmethyl pentasiloxane and a-chloro
phenyl-w--dhloro heptadecamethyl nonaBiloxane are listed in Table 2. Thus,
it was proved that telomer homologs of the a-chloro methyl phenyl siloxy-
w-chloro dimethyl siloxane series are formed by the reaction of octa-
methyl cyclotetraoiloxane with methyl phenyl dichloro silane. There are
4 tables and 3 Soviet references.
ASSOCIATIONi InBtitut elementoorganicheskikh soyedineniy Akademii nauk
SSSR (Institute of Elemental Organic Compounds of the Acad
of Sciences USSR)
SUBMITTED: March 23, 1961
Legend to Tables 1 and 2: (1) Formula; (2) boiling point, OC (p mmHg)j
(3) calculated; (4) found.
Card

S/062/61/000/010/007/018
B117/B101
trialkyl(aryl)hydroxy silanes with methyl
methyl esters of dimethyl phosphinia acid
TEXTs The authors investigated the substitution of the alkoxy group by
dimethyl phosphinio acid radicals as the end groups on various organo-
silicon compounds. It was found that by heating dimethyl ethoxy silyl
methyl eater of dimethyl phosphinic acid with triethyl hydroxy silane at
a ratio of 1:1, ethyl alcohol was separated at 1400 - 1500C and 1-triethyl-
3-dimethyl disiloxane methyl ester of dimethyl phosphinic acid was formed
in 60% yield. From the reaction of dimethyl ethoxy sily1methyl ester of
dimethyl phosphinic acid with dimethyl phenyl hydroxy silane or with
methyl diphenyl hydroxy silane, 1-dimethyl phenyl-3-dimethyl disiloxane
methyl ester of' dimethyl phosphinic acid and 1-methyl diphenyl-3-dimethyl
disiloxane methyl eater of dimethyl phosphinic acid, respectively, were obtained.

28272 5/062/61/000/010/007/018
Reaction of trialkyl... B117 B101
Not only one but two ethoxy groups are substituted on the silicon atom.
Thun, from the reaction of dimethyl phenyl hydroxy silane with methyl di-
ethoxy silyl methyl eater of dimethyl phosphinic acid at a ratio of 211,
1,5-dimethyl phenyl-3-methyl trisiloxane methyl ester of dimethyl
phosphinic acid was obtained. Similar reactions were conducted with tri-
ethyl- and dimethyl diphenyl hydrvxy silanes. All reactions were con-
ducted without a catalyst. The dimethyl phenyl hydroxy silane and methyl
diphenyl hydroxy silane used were produced by the method of
K. A. Andrianov and N. Delazari (Ref. 3: Dokl. AN SSSR 122, 3, 393 (1958)),
and dimethyl ethoxy silyl methyl ester and methyl diethoxy silyl methyl
ester of dimethyl phosphinic acid by the authors' method described in
Ref. 4 (Izv. AN SSSR, Otd. khim. n. 1961, 1454). Ethyl alcohol produced
during the reaction was distilled off and identified on the basis of
boiling temperature and refractive index.. Reactions conducted yielded
compounds not yet described with 2 or 3 silicon atoms containing a di-
methyl phosphinic group. The compounds obtained are colorless liquids
readily soluble in organic solvents and may be distilled in vacuum. Their
properties are listed in the table. There are 1 table and 4 referencest
2 Soviet and 2 non-Soviet,
Card 2/4

28272 S/062/61/000/dlO/007/018
Reaction of trialkyl ... B117/BlOl
ASSOCIATIONs Inatitut elementoorganioheakikh eoyedineniy Akademii nauk
SSSR (Institute of Elemental Organic Compounds of the
Academy of Sciences USSR)
SUBMITTEDt April 6, 1961
Legend to the Tables (1) numberi (2) structural formulai (3) boiling
point, OC (p mm Hg); (4) found; (5) calculated.
'Card 3/4

140 S/191/61/000/011/003/0
B110/B147
AUTHORS: Andrianov, K. A., Pakhomov, V. I., Lapteval N. Ye.
TITLE: Reactions of hydroxy-methyl-mathyl siloxanee with acids and
isooyanates
PERIODICAL: Plastioheskiye massy, no. 11, 1961, 17-20
TEXT: The stability of the hydroxyl group being in a-position to the
Si atom, and its reaction with acids and inocyanates is investigated on
the example of bio~-(hydroxy-methyl)-tetramethyl disiloxane (A) and
poly-(hydroxy-mothyl-methyl)-ailoxane (B). For the preparation of A
according to CH 3COOCH 2(CH3)2 Si-O-Si(CH3)2 CH2OOCCH3+ 20H3OH
HCl z- HOCH2 (CH 3)2S'_0_S'(CH3)2CH2OH +2CH 3COOCH5 , 60 g of bis-(acetoxy-
methyl)-tetramethyl disiloxane were methanolized by means of 240 ml
CH3OH with 1-1.2 %,, HC1. 5 g of anion exchanger A"-2~ (AN-2F) or XH-18
(AN-18) in the OH form lower the HC1 content to 0-05-0.02 %. The yield of
Card 1 1A ,-- -

26967 S/191/61/000/011/003/008
Reactions of hydroxy-methyl-methyl... B110/B147
unpurified A is 91 % of the theoretical amount (45-7 g): n 20 -1-4355;
25. D
d4 0-7989; OH content .16-47 %; Si content -29A6 %; NW- 210.
Rectification at 5-10 -1 -mm Hg produced crystalline, pure A (melting point
,J80C). (Table 1). Experiments proved a comparatively difficult condense-
tion of the hydroxyl groups of A (Table 2). Only when small amounts of
acid are introduced into A, its properties change slowly. Heating of A
for 15 hr at 20000 lowbrs the OH content from 16.95 -to 14.36 %.
Esterification of 6.98 g of A by means of 5.26 g of adipic acid (molar
ratio 1:1) proceeded readily at 200OC:
zH0CH,(CHs)%Si_0_Sj(CH,LCH,0II + xH00QCH,)dC00H
IOICH,(Cti,),SI-O-SI(Clia),CiliOOC(CH,),COOI.,Ii + (2x - I)HO
The ester number increases quickly during polycondensation, the acid
number drops after 15 hr of heating. The polymer with acid number 8-3,
ester number 338, and MW 9500 -was a viscous, highly sticky brown liquid,
soluble in alcohols, ethers, hydrocarbons, ketones, dioxane,-tatrahydro-
furan, acetic acid,..and formic acid. The polyester was treated at 2000C
Card 2/ 7

S/191/61/000/011/003/008
Reactions of hydtoxy-methyl-methyl... D110/1147
and 10 mm Hg with 0-37 g of A for eaterification of the terminal COOH
roupa. 2.023 g of polyester with 0.0516 g of hexamethylene diisocyanate
(0-5 g-mole to I COOH group) at 2000C in io ~. acetic acid solution in
M
the N 2 flow produced an elastic,-rubber;.like polymer:
iiotcii~CH,)'.~1-0-SI(CH,),CilooD(CAijcoo],Cll,(CH,),Si-o-S[(CH.),CHOH+OCN(Cili),NCO
HOICH,(Cli,).SI-O-'SI(Cli,),CII,000(Cli,),CDOI.,Cll,(CH,),SJ-O-SI(CIIS)OC[i,00Wil(CHJ,NCO HT.A.
This dissolves in acetic wid and formic acid, and swelle in tetrahydro-
furan, dioxane, hydrocarbons, and pyridine- 3.06 g of A at 12boC with
2.7'g of C form sticky, elastic polymers well adhering to glass and
duralumin in 1.5 % alcoholic solution. 3.4 g of A at 1200C with 2.9 g of
p-toluylene diisocyana~~q form solid polymers in t,% acetic acid solution
1. xlioCtl,(CH,~SI-O-Sf(Clis)zC4i,,OH + xM,N(CIi,),NCo
xliOCtl,(CH.),SI-O-SI(CH,,~CIICA)CNH-(Ctlo,Nco
C11
11. xIIOCH2(CH.,),SI - 0--SI(CI 1,),CHOli + xMN NICO
Card 3/7

28987 S/191/61/000/011/003/008
Reactions of hydroxy-methyl-methyl... B110/B147
CH**
X"OC' 110'411S' -0- S1P134CH,(X)CN14 NCO
I dissolver in aliphatic alcohols and cresol, I and II in acetic acid and
formic acid. They awell in pyridine, hydrocarbons, and tetrahydrofurano'
15 g of A were mixed with 50 g of 2 ~* 11C1, stirred at 900C for 15 hr, and
'the content of acetic Acid was determined. It was neutralized by means of
solid NaHCO and determined in %:, Si - 20.51 OH - 3.41 CH -COO - 24..18.
3 3
20 g of A was stored for 48 hr at 200C, and viscosity as'well an
refraotive index were determined (Table 2). After heating 5 g of A at
2000C for 15 hr, the OR content drops from .16.95 to 14-30 %. During the
effect of 0.4 9 of 98 Y2S0 on-15 9 of A, 0 and 11 20 remained nearly
, 4 12 D
unchanged even after a longer effect. When .10.72 g of A was left
standing for 48 hr with 40,98 CH OH acidified with 35 % HCl, the Si and
3
OR content remained pradtically constant. The-same applied when 4.97 9
.of A was left standing for 48 hr with 0.64 g of distilled water.. There
are 4 figures, 4 tables# and 3 references: 1 Soviet and 2*non-Soviet.
L Card 4/7

28?~j 91/61/m/oll/oo/oos
Reactions of hydroxy-methyl-methyl... BIIO/BI47
The two references to English-language publications read as follows:
Speier, J. Am. Chem. Boo., IAt 1474 (1949); Us Pat. 2527590 (1950);
C. A., A5, 2498 (1951).
Table 1. Effect of 2 ~ HC1 and H 2so4 on bio-(acetoxymethyl)-tetramethyl
disiloxane.
Legend: (1) Amount of bis-(aoetoxymethyl)-tetramethyl disiloxanel g;
(2) acid used; (3) experimental conditions; (4) content, %; (5) molecular
weight; (6) acetoxy group cleavage, %; (7) initial bis-(acetoxymethyl)-
tetramethyl disiloxane; (8) designation; (9) amount, ml; (10) time. hr;
(11) temperature, OC; (12) OH groups; (13) 2 % H 2s0 4; (1 4) 2 % HCI.
Table 2. Effect of heating on bis-(hydroxy-methyl)-tetramethyI disiloxane.
Legend: (1) Temperature, OCI (2) time, min; :m'.
(3) viscosity' 120
Card 5/7

S/191/61/000/011,/003/008
Reactions of hydroxy-methyl-methyl ... B110147
For Tables see Cards 7/8 and 8/8.
Card 6/8

29519
S/062/61/000/011/006/012
B103/B147
AUTHORS: Andrianov, K. A. and Volkova, L. M.
TITLE: Reaction of aryl-(alkyl-)amino-methyl-ethoxy silanes with
alkyl-(aryl-)hydroxy silanes
PERIODICAL: Akademiya nauk SSSR. Izvestiya. Otdeleniye khimicheskikh
nauk, no. 11, 1961, 2003 - 20o6
TEXT: The paper deals with the reaction of aryl-(alkyl-)amino-methyl-ethoxy
silanes XCH CH Si(oc 2H5)2 with (a) triethyl-hydroxy silane, (b) dimethyl-
phenyl-hydrgxy3silane, and (c) diethyl-dihydroxy silane, X being C 6H5NH-,
CH CH
(C2H5)2 N-, CIC 6H4NH-, 0 ~M,. It has been found that the introdurbon
'CH2CH 2
of one amino group into the organic radical in alpha position to the Si
atom increases the exchangeability of the alkoxy group for the triethyl-
or dimethyl-phenyl-ailoxy groups. The reaction takes place readily and
without catalysts as follows: XCH 2CH3Si(OC 211 5)2 + 2(C211 5)3Sin
Card 1/0

29519
S/062 61/000/011/006/012
Reaction of aryl-(alkyl-)amino-... B103 B147
CH X
1 2
Siu-Si.0-01i (C H ) + 2C H OH. The interaction of diethyl-amino-
3 1 2 5 3 2 5
CH3
methyl-(methyl-)diethoxy silane and (a) at room temperature results in the
heating of the mixture. If the reaction mixture is heated gradually up to
1500C, more than 70% of alcohol is distilled off. 1, 1, 1, 3, 3, 3-hexa-
ethyl-2-methyl.-2-diethyl-amino-methyl trisiloxane was separated by
fractionation of the reaction products (yield 78.5%). Phenyl-amino-methyl-.
dimethyl-ethoxy silane reacts with b) equally well. Already within the
first hour of heating more than 70% of alcohol was separated and 1, 1, 2, 2-
tetramethyl-l-phenyl-amino-methyl-2-phenyl disiloxane was formed. In the
above cases, one alkoxy group is substituted by the triethyl- or dimethyl-
phenyl-siloxy groups just as readily as two. The reaction of c) with
phenyl-amino-methyl-dimethyl-ethoxy silane is much more complicated. Two
products were separated: 1, 1, 3, 3-tetramethyl-2,2-dieth~,1-1,3-di(phenyl-
amino-methyl) trisiloxane and bis-(phenyl-amino-methyl)-tetramethyl
disiloxane. The reaction does not only take place as follows:
Card 2/0 4

2 19
S/062/619~000/01 1/006/012
Reaction. of aryl-(alkyl-)qmino... B103/B147
hydr'oxy silanes according t"o the following mechunism:
CHI OC41s
-CG1isNHWj(CHJ,0C [Cji ty~S( H
.2"' +OHSI(CW, 3,NHC I .. I ,
C113 Osj(c~to]
C.H.NHW1(CH)j0S'(r1Hd3 + C'"10"
There are 1 table and 3 non-Soviet references. V-e reference to the English-
language publication reads as follows: L. J 0 Tyler, US-Patent 2611774;
23. IX. 1952; Chem. Abstr. AL 4129 (1953).
ASSOCIATION: Institut elementoorganicheskikh soyedineniy Akadeniii nauk SSSR
(Institute of Elemental Organic Compounds of the Academy of
Sciences USS-R)
Card

3a6h
S10621611000101210031012
B118/B147
AUTHORSt Andrianov, K. A., and Delazari, N. V.
TITLEt Reactions of trimethyl siloxychloro silanes
PERIODICALs Akademiya nauk SSSR. Izveatiya. Otdeleniye khimicheskikh
nauk, no. 12, 1961, 2169 - 2173
TEXTs Since reactions of trimethyl siloxychloro silanes with nucleophilic
and electrophilic compounds so far have not been sufficiently studied,
the authors showed in a previous paper the high reactivity of the tri-
methyl siloxy group in bis-(trimethyl siloxy)-dichloro silane where the
Si-O-Si bond is unexpectedly ruptured. In the present work, other reac-
tions of compounds containing a trimethyl siloxy group on the silicon
atom have been studied. It was shown that tris-(trimethyl siloxy)-
hydroxy silane did not react with tetrabutoxy titanium and tin tetra-
chloride on heating for a longer period in the presence of NH 3' When
heated in the presence of HC1, trio-(trimethyl siloxy)-hydroxy silane
does not form a dimer, and the initial product remains unchanged. Reac-
Card 1/4

3,0168
S/062/61/000/012/003/012
Reactions of trimethyl ... B118/B147
tion between NH 3 and bis-(trimethyl siloxy)-dichloro silane in benzene
at room temperature yielded 'two productas bia-(trimethyl siloxy)-diamino-
silane and 1,5-bis-(trimethyl siloxy)-1,3-aminodiailosane according to
the formulas f(OH 3)3S'0]2S'(N 2)2 (1) (53.1%) (boiling point 51 - 530C
20% 20 .
n. d 0.9o66; MR (determined) 64-43) and
/3 mm Hg); 1.4057; 4
CH 3)35 1012 -SIi- NH - SI1 1( CH~P '0]2 (11) (22.2A) (boiling point:
NH2 NH
117 - 1190C (3 mm Hg); n 20 - 1.4119; d20 28). Unlike
D 4 - 0.9338; MR - 122.
hydrolysis, aminolysis yielded no complex, insoluble polymers. Hence,
the trimethyl siloxy group was not separated. Heating compound (I) at
212 - 3040C for a longer period and with liberation of NH 3 yielded the
crystalline compound 1,3-bis-(trimethyl siloxy)-cyclosilosanet
H
CH 3)3S'012S'/*"' Si H ) S '012 (111) (with melting pointi 1030C,
\N1 3 3
Card 214 A

30 6h
3/062 )1/000/012/003/012
Reactions of trimethyl... B118FB147
boiling pointi 180 - 1830C (4 mm 11g)). To confirm its structure, com-
pound (III) was also obtained from 1,3-bis-(trimethyl silov)-1,3-amino-
disilosane by 25 hr heating at 280 - 3440C. Separation of the trimethyl
siloxy group and formation of insoluble products were not observed on
aminolysis. Above 1500C, tris-(trimethyl siloxy)-hydroxy silane reacts
with Na with formation of H., tetrakis-(trimethyl siloxy).-silane,
V CH 3)3Sio]4Si (5% , and tris-(trimethyl siloxy)-sodium oxy-silane (17-9A,-
In the formation of the former, the Si-O-Si bond is ruptured. On heating
tris-(trimethyl siloxy)-hydroxy silane and TiCl 4 for a longer period, no
reaction occurs, whereas reaction between TiCl, and ~(CH-.).SiOj,SiONa
elds tetrakis- rtris-(trimethyl siloxy)siloxyj titanium. -
CH 3)3 SiOj3Si0j4Vi -here the Si-O-Si bond is not ruptured (boiling 6X
20 20
pointj 223 - 2250C (1-5 mm Hg nD . 1.4201; d4 . 0.9623; MR - 341-9).
Irrespective of the high molecular weight and the 80-7~oo inorganic portion,
this compound is an easily mobile liquid. These properties are explained
I
by the cross-type structure -Ti- where the inorganic portion of the
Card 3/4

2
S~ 0'0
062 611001100610021010
D B118/B220
AUTHOR: Andrianov, K. A., Vasillyeva, T. V.)
and Khananashvili, L. M.
TITLEt Condensation of methyl phosphinic acid
with di ethoxy- dime thyl siloxanes
PERIODICAM Akademiya nauk SSSR. Izvestiya.
Otdeleniye khimicheskikh nauk, v. 14, no.. 6, 1961, 1030-1035
TEXTt The present paper deals with the condensation of d.,,,)-diethoxy-
dimethyl siloxanes with methyl phosphinic acid. This reaction proved to
be an easy method of synthesizing the mixed organo-silicon phosphorus
compounds resulting primarily in the formation of cyclic, not high-polymer
compounds. An increase of the distance between the alkoxy groups in
OC r) -diethoxy-dimethyl siloxanes does not alter the direction of the
reaction. In any case, the reaction proceeds according to the following
equation
Card 1/4

25040
S/062/61/001/006/002/010
Condensation of methyl phosphinic ... B118/B220
cyclodi (methyl phosphinoxy) diailoxanes On condensation of methyl.
phosphinic acid with ;