Reaction of organylchlorosilanes with dimethyl sulfoxide in the presence of octamethyltrisiloxane

Article abstract of DOI:10.1023/B:RUGC.0000042423.40451.86

Dichloro(methyl)(vinyl)silane reacts with DMSO in the presence of octamethyltrisiloxane to form cyclooligomethyl(vinyl)siloxanes(MeViSiO) _n (n = 3-6). The reaction involves disproportionation of octamethyltrisiloxane into hexamethyldisiloxane and decamethyltetrasiloxane. Along with the latter two products, insertion products of methyl vinyl silanone into both permethyloligosiloxanes were identified. Alkyltrichlorosilanes RSiCl₃ (R = Me, Et) react with DMSO in the presence of octamethyltrisiloxane to form cyclic oligoalkyltrichlorosiloxanes (RClSiO) _m (m = 3-6).

Full text of DOI:10.1023/B:RUGC.0000042423.40451.86

Russian Journal of General Chemistry, Vol. 74, No. 6, 2004, pp. 882 884. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 6, 2004,
pp. 956 958.
Original Russian Text Copyright
2004 by Basenko, Gebel’, Boyarkina, Voronkov.
Reaction of Organylchlorosilanes with Dimethyl Sulfoxide
in the Presence of Octamethyltrisiloxane
S. V. Basenko, I. A. Gebel’, E. V. Boyarkina, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences, Irkutsk, Russia
Received May 7, 2002
Abstract Dichloro(methyl)(vinyl)silane reacts with DMSO in the presence of octamethyltrisiloxane to
form cyclooligomethyl(vinyl)siloxanes(MeViSiO)n (n = 3 6). The reaction involves disproportionation of
octamethyltrisiloxane into hexamethyldisiloxane and decamethyltetrasiloxane. Along with the latter two
products, insertion products of methyl vinyl silanone into both permethyloligosiloxanes were identified. Alkyl-
trichlorosilanes RSiCl3 (R = Me, Et) react with DMSO in the presence of octamethyltrisiloxane to form cyclic
oligoalkyltrichlorosiloxanes (RClSiO)m (m = 3 6).
Previously we showed that the reaction of dior-
ganyldichloro- and organyltrichlorosilanes with
DMSO in a hexamethyldisiloxane (I) medium is a
convenient synthetic route to linear and cyclic organyl-
(trimethylsiloxy)siloxanes [1, 2].
(1:1:3 reagent molar ratio), the yield of cyclomethyl-
(vinyl)siloxanes IV VII is almost the same.
Under the reaction conditions, trisiloxane II under-
goes disproportionation into disiloxane I and de-
camethyltetrasiloxane (X). Neither MeVinSiCl2 nor
DMSO taken separately induce disproportionation of
compound II.
The major products of reaction (1) between di-
chloro(methyl)(vinyl)silane with DMSO in the
presence of octamethyltrisiloxane (II) that serves for
trapping the intermediate methyl vinyl silanone (III),
at 20 C and a 1:1:1 reagent molar ratio are cyclo-
methyl(vinyl)siloxanes (MeViSiO)n (IV VII, n = 3
6) in a total yield of 75 80%. Therewith, the yield of
insertion products of methyl vinyl silanone into tri-
siloxane II, namely 1,1,1,3,5,5,7,7,7-nonamethyl-3-
vinyltetrasiloxane (VIII) and 1,1,1,3,5,7,7,9,9,9-de-
camethyl-3,5-divinylpentasiloxane (IX), is as low
as 3 5%.
2Me3SiOSiMe2OSiMe3
II
Me3SiOSiMe3 + Me3SiOSiMe2OSiMe2OSiMe3. (4)
I
X
Siloxanes I and X were isolated and characterized
by GC MS, along with insertion products of silanone
III into disiloxane I [1,1,1,3,5,5,5-heptamethyl-3-
vinyltrisiloxane (XI), 1,1,1,3,5,7,7,7-octamethyl-3,5-
divinyltetrasiloxane (XII), 1,1,1,3,5,7,9,9,9-nona-
methyl-3,5,7-trivinylpentasiloxane (XIII)] and into
decamethyltetrasiloxane [1,1,1,3,5,5,7,7,9,9,9-unde-
camethyl-3-vinylpentasiloxane (XIV)].
CH3(CH2=CH)SiCl2 + OS(CH3)2
(1)
(2)
[CH3(CH2=CH)Si=O] + S(CH2Cl)CH3,
HCl
III
n[MeVinSi=O]
III
(MeVinSiO)n,
IV VII
I + III
Me3SiO(MeVinSiO)nSiMe3,
(5)
XI XIII
m[MeVinSi=O] + Me3SiOSiMe2OSiMe3
II
n = 1 (XI), 2 (XII), 3 (XIII).
III + Me3SiOSiMe2OSiMe2OSiMe3
Me3SiOSiMe2O(MeVinSiO)mSiMe3,
(3)
X
VIII, IX
Me3SiOSiMe2OSiMe2O(MeVinSiO)SiMe3.
(6)
n = 3 (IV), 4 (V), 5 (VI), 6 (VII); m = 1 (VIII), 2 (IX).
XIV
Reaction (2) between MeVinSiCl2 and DMSO can
occur in the absence of trisiloxane II [1], and the yield
of compounds IV VII is slightly higher. At higher
concentrations of trisiloxane II in the reaction mixture
Insertion products XI XIII we also identified
earlier in the reaction of MeVinSiCl2 with DMSO and
disiloxane I [1].
1070-3632/04/7406-0882 2004 MAIK Nauka/Interperiodica

REACTION OF ORGANYLCHLOROSILANES WITH DIMETHYL SULFOXIDE
883
Mass spectra of Me3Si(OSiMeVin)n(OSiMe2)mOSiMe3 (VIII, IX, XI XIV) [n = 1, m = 1 (VIII); n = 2, m = 1 (IX); n = 1,
m = 0 (XI); n = 2, m = 0 (XII); n = 3, m = 0 (XIII); n = 1, m = 2 (XIV)]
m/z (Irel, %)
Ion
VIII
IX
XI
XII
XIII
XIV
[M
[M
[M
[M
Me]+
307 (60)
221 (42)
219 (80)
207 (100)
393 (33)
307 (3)
305 (36)
293 (100)
159 (55)
147 (41)
233 (100)
147 (8)
145 (4)
133 (17)
159 (3)
147 (7)
133 (10)
85 (30)
73 (68)
59 (10)
319 (52)
233 (7)
231 (25)
219 (100)
159 (1)
147 (2)
133 (5)
85 (85)
73 (80)
59 (23)
405 (47)
319 (7)
381 (12)
295 (9)
293 (86)
281 (100)
OSiMe2Vin]+
Me
Vin
Me4Si]+
Me4Si]+
317 (19)
305 (85)
159 (77)
147 (29)
133 (10)
85 (80)
[Me3SiOSiMeVin]+
[Me3SiOSiMe2]+
[Me3SiOSiMeH]+
[Me2VinSi]+
147 (2)
133 (2)
85 (32)
73 (62)
59 (7)
147 (12)
73 (9)
85 (36)
73 (59)
59 (12)
[Me3Si]+
73 (100)
59 (32)
[Me2SiH]+
The reaction of organyltrichlorosilanes RSiCl3 (R =
Me, Et) with DMSO in the presence of trisiloxane II
(1:1:1 molar ratio) at 20 C gives no cycloorganyl-
(trimethylsiloxy)siloxanes [R(Me3SiO)SiO]n that form
in a high yield in the disiloxane I medium. The major
products of the former reaction are cyclic oligoalkyl-
chlorosiloxanes (RClSiO)m (XV XXI, m = 3 6)
whose yields reach 80%. Their formation can be ex-
plained in terms of cyclization of the intermediate
alkyl chlorosilanones.
chloro(methyl)(vinyl)silane and 23.6 g of octamethyl-
trisiloxane, placed in a 50-ml flask equipped with a
long Vigreux column. The mixture was heated to the
boil. Therewith, 4.3 g (44%) of chloromethyl methyl
sulfide distilled, bp 109 110 C, n2D0 1.4965 (bp 110
112 C [3]). Found, %: C 25.25; H 5.24; Cl 36.94; S
32.85. C2H5ClS. Calculated, % : C 24.87; H 5.22; Cl
36.71; S 33.20. Along with chloromethyl methyl
sulfide, dimethyl sulfide formed. Vacuum distillation
of the residue gave a fraction [8.2 g (95%)] with bp
70 200 C (6 mm). It was subjected to GC MS
analysis. The resulting data are presented in the table.
The mass spectra of (MeVinSiO)n (n = 3 6) have
been reported in [4].
m[RClSi=O]
(RClSiO)m,
(7)
XV XXI
R = Me, m = 3 (XV), 4 (XVI), 5 (XVII); R = Et, m = 3
(XVIII), 4 (XIX), 5 (XX), 6 (XXI).
The reactions of Me2SO with MeVinSiCl2 in the
presence of trisiloxane II (1:1:3 molar ratio) and
with RSiCl3 were performed in a similar way. In the
latter case, compounds XV XXI were obtained.
EXPERIMENTAL
Gas chromatography mass spectrometry was per-
formed on an LKB-2091 GC MS system at an ioniz-
ing voltage of 60 V, using an SE-54 capillary column,
length 38 m. The oven temperature was raised at a
rate of 16 deg/min to 270 C. Accelerating voltage
2 kV. The m/z values for chlorine-containing ions
relate to 35Cl. The intensity ratio for isotope peaks is
consistent with calculation.
Compound XV. Mass spectrum, m/z (Irel, %): 267
(100) [M Me]+, 247 (11) [M Cl]+, 173 (10) [M
Me
Me(Cl)SiO]+, 113 (16) [MeSiCl2]+, 93 (4)
[Me2SiCl]+, 79 (12) [M
Me
2 Me(Cl)SiO]+.
Compound XVI. Mass spectrum, m/z (Irel, %): 361
(100) [M Me]+, 341 (11) [M Cl]+, 267 (13) [M
Me Me(Cl)SiO]+, 173 (8) [M Me 2Me(Cl)SiO]+,
113 (15) [MeSiCl2]+, 93 (24) [Me2SiCl]+.
Dimethyl sulfoxide was kept over melted KOH,
decanted, frozen, and distilled in a vacuum. Dichloro-
(methyl)(vinyl)silane was purified by column rectifica-
tion.
Compound XVII. Mass spectrum, m/z (Irel, %):
455 (65) [M Me]+, 435 (21) [M Cl]+, 361 (17)
[M
Me
Me(Cl)SiO]+, 267 (100) [M
Me
2Me(Cl)SiO]+, 113 (25) [MeSiCl2]+, 93 (74)
[Me2SiCl]+.
Reaction of dimethyl sulfoxide with dichloro-
(methyl)(vinyl)silane in the presence of octame-
thyltrisiloxane (II). Dimethyl sulfoxide, 7.8 g, was
added dropwise with cooling (0 C) to 14.1 g of di-
Compound XVIII. Mass spectrum, m/z (Irel, %):
295 (100) [M Et]+, 267 (34) [M 2Et + H]+, 187 (1)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 6 2004

884
BASENKO et al.
[M Et Et(Cl)SiO]+, 127 (2) [EtSiCl2]+, 121 (4)
2Et(Cl)SiO]+, 295 (75) [M Et 3Et(Cl)SiO]+, 127
[Et2SiCl]+.
(11) [EtSiCl2]+, 121 (33) [Et2SiCl]+.
Compound XIX. Mass spectrum, m/z (Irel, %): 403
(100) [M Et]+, 375 (34) [M 2Et + H]+, 295 (31)
[M Et Et(Cl)SiO]+, 187 (4) [M Et 2Et(Cl)SiO]+,
127 (12) [EtSiCl2]+, 121 (14) [Et2SiCl]+.
REFERENCES
1. Basenko, S.V., Gebel’, I.A., Voronkov, M.G., Kly-
ba, L.V., and Mirskov, R.G., Izv. Ross. Akad. Nauk, Ser.
Khim., 1998, no. 8, p. 1614.
Compound XX. Mass spectrum, m/z (Irel, %): 511
(100) [M Et]+, 483 (14) [M 2 Et + H]+, 403 (11)
[M Et Et(Cl)SiO]+, 295 (4) [M Et 2Et(Cl)SiO]+,
127 (11) [EtSiCl2]+, 121 (34) [Et2SiCl]+.
2. Basenko, S.V., Gebel’, I.A., and Voronkov, M.G., Izv.
Ross. Akad. Nauk, Ser. Khim., 2000, no. 2, p. 361.
3. Bohme, H., Fisher, H., and Frank, R., Justus Liebigs
Ann. Chem., 1949, vol. 563, nos. 1 3, p. 54.
Compound XXI. Mass spectrum, m/z (Irel, %): 619
(60) [M Et]+, 591 (14) [M 2Et + H]+, 511 (61)
4. Polivanov, A.N., Bernadskii, A.A., Bochkarev, V.N.,
Zhun’, V.I., and Sheludyakov, V.D., Zh. Obshch. Khim.,
1980, vol. 50, no. 3, p. 614.
[M
Et
Et(Cl)SiO]+, 403 (100) [M
Et
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 6 2004