881
SILYLATED DERIVATIVES OF AZASILACYCLOPENTANES
ppm: 0.09 s (9Н, NSiMe3), 0.56 t (2H, C3H2, 3J 7.7 Hz),
1.78 t. t (2H, C4H2, 3J 7.7, 6.9 Hz), 2.91 t (2H, C5H2, 3J
6.2 Hz), 3.47 s (6H, MeO). 13С NMR spectrum (100.6
MHz, CDCl3), δC, ppm: –1.11 (NSiMe3), 4.12 (C3),
24.89 (C4), 44.86 (C5), 49.65 (MeO). 29Si NMR spec-
trum (79.5 MHz, CDCl3), δSi, ppm: 2.49 (NSiMe3),
–14.30 (Si2).
in vacuum. Yield of distilled product XIV 210.50 g
(88.8%), purity of 97%, mp 138–139°С (85 mmHg),
nD20 1.4238. H NMR spectrum (300 MHz, СDCl3), δ,
1
ppm: 0.11 s (9H, OSiMe3), 0.51–0.58 m (2Н, С1Н2),
1.43–1.53 m (2Н, С2Н2), 1.15 br.s (2H, NH2), 2.63 t
3
(2Н, С3Н2, J 7.0 Hz), 3.48 s (6H, MeO). 29Si NMR
spectrum (59.6 MHz, CDCl3), δSi, ppm: –49.81 (Si),
8.59 (ОSiМе3).
1-(Trimethylsilyl)-2-methoxy-2-trimethylsiloxy-
1-aza-2-silacyclopentane (XII). A mixture of 237.06 g
(1 mol) of 1,1,1-trimethyl-3,3-dimethoxy-3-(3-amino-
propyl)disiloxane XIV, 161.02 g (1 mol) of hexa-
methyldisilazane III, and 3.98 g of ammonium
chloride (1%) was incubated at 120°С during 20 h.
Trimethylmethoxysilane was distilled off during the
reaction. Yield of distilled product XII 194.45 g
(70.2%), purity of 98%, mp 149–150°С (85 mmHg),
Silane (XI). 1H NMR spectrum (300 MHz, СDCl3),
δ, ppm: 0.58–0.65 m (2H, C1H2), 1.25 br.s (2H, H2N),
3
1.47–1.57 m (2H, C2H2), 2.65 t (2H, C3H2, J 7.0 Hz),
3.54 s (9H, MeO). 29Si NMR spectrum (59.6 MHz,
CDCl3): δSi –42.45 ppm (Si).
1,1,1,3-Tetramethyl-3-methoxy-3-(3-amino-
propyl)disiloxane (XV). 90.00 g (1 mol) of trimethyl-
silanol was added dropwise to 163.06 g (1 mol) of 3-
aminopropylmethyldimethoxysilane IV during 3 h at
room temperature. The formed methanol was distilled
off in vacuum. Yield of distilled product XV 189.2 g
(85.6%), purity of 99%, mp 88–89°С (15 mmHg), nD20
1.4251. 1H NMR spectrum (300 MHz, СDCl3), δ, ppm:
0.03 s (3Н, Me), 0.08 s (9H, OSiMe3), 0.48–0.54 m
(2Н, С1Н2), 1.40–1.50 m (2Н, С2Н2), 1.61 br.s (2H,
nD20 1.4270. H NMR spectrum (400 MHz, СDCl3), δ,
1
ppm: 0.03 s (9H, OSiMe3), 0.00 s (9Н, NSiMe3), 0.31
d.t (1H, C3H, 2J 15.0, 3J 7.6 Hz), 0.50 d.t (1H, C3H', 2J
3
15.0, J 7.6 Hz), 1.61–1.73 m (2H, C4H2), 2.80 t (2H,
3
C5H2, J 6.1 Hz), 3.34 s (3H, MeO). 13С NMR spec-
trum (100.6 MHz, CDCl3), δC, ppm: –0.73 (NSiMe3),
1.46 (OSiMe3), 6.63 (C3), 25.08 (C4), 44.93 (C5), 49.75
(MeO). 29Si NMR spectrum (79.5 MHz, CDCl3), δSi,
ppm: –23.72 (Si2), 2.14 (NSiMe3), 8.21 (OSiMe3).
3
NH2), 2.64 t (2Н, С3Н2, J 7.0 Hz), 3.43 s (3H, MeO).
29Si NMR spectrum (59.6 MHz, CDCl3), δSi, ppm: –
12.75 (Si), 6.36 (ОSiМе3).
1-(Trimethylsilyl)-2-methyl-2-trimethylsiloxy-1-
aza-2-silacyclopentane (XIII). A mixture of 221.04 g
(1 mol) of 1,1,1,3-tetramethyl-3-methoxy-3-(3-amino-
propyl)disiloxane XV, 161.04 g (1 mol) of hexa-
methyldisilazane III, and 3.82 g of ammonium
chloride (1%) was incubated at 125°С during 24 h.
Trimethylmethoxysilane was distilled off during the
reaction. Yield of distilled product XIII 184.53 g
(70.7%), purity of 97%, mp 99–100°С (17 mmHg),
Silane (IV). 1H NMR spectrum (300 MHz, СDCl3),
δ, ppm: –0.10 s (3H, Me), 0.37–0.45 m (2H, C1H2),
0.93 br.s (2H, H2N), 1.23–1.35 m (2H, C2H2), 2.46 t
3
(2H, C3H2, J 7.0 Hz), 3.30 s (6H, MeO). 29Si NMR
spectrum (59.6 MHz, CDCl3): δSi –2.61 ppm (Si).
2,2'-Oxybis-[1-(trimethylsilyl)-2-methyl-1-aza-2-
silacyclopentane] (XVI). A mixture of 203.03 g
(1 mol) of 1-(trimethylsilyl)-2-methyl-2-methoxy-1-
aza-2-silacyclopentane V, 261.02 g (1 mol) of 1-(tri-
methylsilyl)-2-methyl-2-trimethylsiloxy-1-aza-2-sila-
cyclopentane XIII, and 3.25 g of sodium trimethyl-
silanolate (0.7%) was incubated at 160°С during 15 h.
Trimethylmethoxysilane was distilled off during the
reaction. Yield of the distilled product XVI 86.40 g
(24%), purity of 97%, mp 116–117°С (2 mmHg), nD20
1.4580. 1Н NMR spectrum (400 MHz, СDCl3), δ, ppm:
0.06 s (18Н, N1SiMe3, N1'SiMe3), 0.16 s (6H, Si2Me,
nD20 1.4295. H NMR spectrum (300 MHz, СDCl3), δ,
1
ppm: 0.08 s (9Н, OSiMe3), 0.078 s (9H, NSiMe3), 0.16
s (3H, Me), 0.46 d.t (1H, C3H, 2J 14.0, 3J 8.0 Hz), 0.58
2
3
d.t (1H, C3H', J 14.0, J 6.9 Hz), 1.69–1.79 m (2H,
C4H2), 2.83 d.t (1H, C5H, J 10.0, J 6.5 Hz), 3.00 d.t
2
3
(1H, C5H', J 9.9, J 5.7 Hz). 13С NMR spectrum
(75.5 MHz, CDCl3), δC, ppm: –0.03 (NSiMe3), 1.12
(Me), 1.93 (OSiMe3), 12.68 (C3), 25.78 (C4), 46.92
(C5). 29Si NMR spectrum (59.6 MHz, CDCl3), δSi,
ppm: 2.08 (NSiМе3), 6.12 (ОSiМе3), 1.72 (Si2).
2
3
2
3
Si2'Me), 0.45 d.t. (2H, C3H, C3'H, J 14.0, J 8.0 Hz),
2
3
1,1,1-Trimethyl-3,3-dimethoxy-3-(3-amino-
propyl)disiloxane (XIV). 90.00 g (1 mol) of tri-
methylsilanol was added dropwise to 179.02 g (1 mol)
of 3-aminopropyltrimethoxysilane XI during 3 h at
room temperature. The formed methanol was distilled
0.60 and 0.61 d.t (2H, C3H', C3'H', J 14.0, J 7.0 Hz),
1.69–1.76 m (4H, C4H2, C4'H2), 2.82 d.t (2H, C5H,
C5'H, J 14.0, J 6.2 Hz), 2.99 d.t (2H, C5H', C5'H', J
2
3
2
10.0, J 5.9 Hz). 13С NMR spectrum (100.6 MHz,
3
CDCl3), δC, ppm: –0.09 (NSiMe3), 0.96 (Si2Me), 1.02
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 5 2014