548
ZUEV, KALININ
since the relative content of possible isomers (A,
eeeee; B, aeeee; C, aaeee; D, aeaee) and the popula-
tion of conformers of isomers C and D are unknown.
The 29Si NMR spectrum of cyclopentasiloxane
N4D consists of three lines assignable to fragment D
( 19.45, 20.06, 21.08 ppm) and three lines assign-
able to fragment N ( 23.55, 24.22, 25.10 ppm).
CH2CN). 13C NMR spectrum, C, ppm: 0.03
(CH3 Si), 13.81 (CH3), 15.01 (SiCH2), 15.97
(CH2CN), 16.34 (OCH2), 27.33 (CH3CH2), 28.14
(OCH2CH2), 121.96 (CN). Found, %: C 47.02; H
8.15; N 1.83; Si 4.15. C28H61NO2SiSn2. Calculated,
%: C 47.41; H 8.67; N 1.97; Si 3.96.
Methyl( -cyanoethyl)cyclosiloxanes IV and Va
Vc. Equimolar amounts of I or II and appropriate , -
dichlorosilane III in THF (20 ml of solvent per 2 g of
reactants) were stirred at room temperature for 4 h.
Then the solvent was distilled off, and tributylchloro-
stannane was distilled off in a vacuum. The residue
was vacuum-distilled.
Thus, we have prepared previously unknown
(methyl- -cyanoethyl)tri-, tetra-, and pentacyclosilox-
anes by oxygen halogen exchange between silicon
and tin.
EXPERIMENTAL
Trimethyltris( -cyanoethyl)cyclotrisiloxane IVa.
The IR spectra were taken on a Bruker IFS-88
spectrophotometer (liquid samples on KBr lens). The
NMR spectra were recorded on a Bruker DPX-300 or
Bruker AM-500 (for Si) spectrometer (solvent CDCl3,
internal reference TMS; working frequencies, MHz:
Yield 86%; colorless transparent liquid, bp 215 C
(1 mm Hg), n1D8 1.4682, d240 1.2225. IR spectrum, ,
1
cm : 2965, 2930, 2906 (CH3), 2245 (CN), 1017
1
(Si O Si). H NMR spectrum, , ppm: 0.21 s (3H,
CH3 Si), 0.81 t (2H, CH2 Si), 2.21 t (2H, CH2CN).
13C NMR spectrum, C, ppm: 0.50 (CH3 Si), 10.67
(SiCH2), 12.32 (CH2CN), 120.89 (CN). Found, %:
C 43.00; H 6.37; N 12.95; Si 24.57. C12H21N3O3Si3.
Calculated, %: C 42.45; H 6.29; N 12.48; Si 24.81.
1H 300.13; 13C, 13C {1H} 75.468; 29Si, 29Si {1H}
59.627 or 99.378). The refractive index was deter-
mined with an IFS-22 Abbe refractometer.
Hexabutyldistannoxane was prepared according to
[9]. , -Dichloro(methyl- -cyanoethyl)oligosiloxanes
II were prepared according to [11].
Tetramethyltetrakis( -cyanoethyl)cyclotetra-
siloxane IVb. Yield 86%; colorless transparent liquid,
bp 242 C (1 mm), n1D8 1.4642, d240 1.2219. IR
Bis(tri-n-butylstannyloxy)dimethylsilane Ia.
Hexabutyldistannoxane, 13.86 g, was slowly added
dropwise with stirring to 3.0 g of dimethyldichloro-
silane. The reaction mixture strongly warmed up. After
adding the whole amount of hexabutyldistannoxane,
the mixture was heated to 180 C for 4 h and then
distilled in a vacuum. Tributylchlorostannane was
distilled first. Yield of compound Ia 1.25 g (81%);
1
spectrum, , cm : 2970, 2936, 2906 (CH3), 2251
1
(CN), 1430, 1083 (Si O Si). H NMR spectrum, ,
ppm: 0.02 0.05 set of singlets (3H, CH3 Si), 0.76 m
(2H, CH2 Si), 2.19 m (2H, CH2CN). 13C NMR spec-
trum, C, ppm: 0.63 (CH3 Si), 10.86 (SiCH2),
12.42, 12.56, 12.74, 12.90 (CH2CN), 120.89 (CN).
Found, %: C 40.51; H 6.47; N 12.38; Si 26.01.
C15H28N4O4Si4. Calculated, %: C 40.88; H 6.31;
N 12.71; Si 25.49.
transparent colorless liquid, bp 195 C (1 mm), nD18
1
1.4718, d240 1.1806. IR spectrum, , cm : 2960, 2932,
1
2870, 2855 (CH3), 1460, 1245, 976, 513 (Sn O). H
Pentamethylpentakis( -cyanoethyl)cyclopenta-
siloxane IVc. Yield 81%; transparent yellowish liquid,
bp 280 C (1 mm), n1D8 1.4637, d240 1.2215. IR
NMR spectrum, , ppm: 0.03 s (6H, CH3 Si), 0.92 t
(18H, CH3), 1.04 t (12H, CH2O), 1.32 m (12H,
CH3CH2), 1.56 m (12H, OCH2CH2). 13C NMR spec-
trum, C, ppm: 0.58 (CH3 Si), 13.13 (CH3), 15.61
(OCH2), 26.65 (CH3CH2), 27.46 (OCH2CH2). Found,
%: C 46.11; H 8.97; Si 4.02. C26H60O2SiSn2. Cal-
culated, %: C 46.59; H 9.02; Si 4.19.
1
spectrum, , cm : 2970, 2936, 2906 (CH3), 2251
1
(CN), 1430, 1080 (Si O Si). H NMR spectrum, ,
ppm: 0.02 0.05 set of singlets (3H, CH3 Si), 0.75 m
(2H, CH2 Si), 2.20 m (2H, CH2CN). 13C NMR spec-
trum, C, ppm: 0.62 (CH3 Si), 10.84 (SiCH2),
12.37, 12.58, 12.78, 12.90 (CH2CN), 120.89 (CN).
Found, %: C 40.11; H 6.60; N 13.02; Si 26.17.
C18H35N5O5Si5. Calculated, %: C 39.88; H 6.51;
N 12.92; Si 25.91.
Bis(tributylstannyloxy)methyl- -cyanoethyl-
silane Ib was prepared similarly starting from methyl-
-cyanoethyldichlorosilane. Yield 75%; light yellow
liquid, bp 232 C (2 mm), n1D8 1.4847, d420 1.1918. IR
1
spectrum, , cm : 2959, 2920, 2870, 2854 (CH3),
Tetramethylbis( -cyanoethyl)cyclotrisiloxane
1
1460, 1245, 990, 510 (Sn O). H NMR spectrum, ,
Va. Yield 91%; transparent colorless liquid, bp 195 C
ppm: 0.09 s (3H, CH3 Si), 0.70 t (2H, CH2 Si),
0.92 t (18H, CH3), 1.06 t (12H, CH2O), 1.32 m (12H,
CH3CH2), 1.58 m (12H, OCH2CH2), 2.20 t (2H,
(1 mm), n1D8 1.4415, d240 1.0561. IR spectrum,
,
1
cm : 2964, 2930, 2907 (CH3), 2249 (CN), 1263,
1
1020 (Si O Si). H NMR spectrum, , ppm: 0.10 s
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 4 2003