ChruÑciel
1407
cooled to room temperature, and left overnight. Solids were
filtered off, washed with dry ether. The filtrate was fraction-
ally distilled to give an ether fraction and 21.8 g (43% yield)
of (CH2)4NSiMe2H (bp 47–48°C/40 mmHg).
4.88 (sept., 1H, Si-H); in CCl4: 0.45 (d, J = 3.0 Hz, 6H,
(CH3)2Si), 4.80 (sept., J = 3.0 Hz, 1H, Si-H).
Et2NSiMe2Cl
Boiling point 152–154°C. 1H NMR: 0.38 (s, 6H, (CH3)2Si),
0.98 (t, J = 7 Hz, 6H, CH3-C), 2.85 (q, J = 7 Hz, 4H, CH2-N).
Reaction of (pyrrolidino)dimethylsilane with
dimethyldichlorosilane
Into a 250 mL two-neck flask was placed 18.1 g (0.14
mol) of (pyrrolidino)dimethylsilane and 34 mL (0.28 mol) of
dimethyldichlorosilane. The reaction flask was heated to re-
flux, and HMe2SiCl (with traces of Me2SiCl2) was
continously distilled off through a Vigreux columnto give
9.0 g (68% yield) of HMe2SiCl (bp 36°C). Distillation of the
residue gave (CH2)4NSiMe2Cl (17.1 g, 74% yield; bp 80–
81°C/40 mmHg).
Et2NSiMe2(H)
Boiling point 111–112°C. IR (neat (cm–1)): 2120 (Si-H).
1H NMR (300 MHz, CDCl3, δ (ppm)): 0.185 (d, 6H, J =
2.79 Hz, (CH3)2Si), 1.11 (t, 6H, J = 7.14 Hz, CH3-C), 2.65
(q, 4H, J = 7.15 Hz, CH2-N), 4.68 (sept., 1H, J = 2.78 Hz,
Si-H). 13C NMR: –1.49 (s, CH3-Si), 15.63 (s, CH3), 41.00 (s,
CH2-N). 29Si NMR: –7.77 (s).
Et2NSiMePhCl
Boiling point 136–140°C/25 mmHg, 108–110°C/5 mmHg.
n2D0 1.5073. IR (neat (cm–1)): 3068, 1800–2000, 1588 (Ph),
1426 (Si-Ph), 1253 (Si- CH3), 2966, 2927, 2866 (C-H aliphat.),
1202, 1166, 1055 (C-N), 1028, 931 (Si-N), 640, 460, 413
Preparation of (diethylamino)methylphenylchlorosilane
Into a 1.5 L four-neck reactor, fitted with a condenser and
a mechanical stirrer, was placed 116.3 mL (0.72 mol) of
methylphenyldichlorosilane and 900 mL of dry ether.
151 mL (1.46 mol) of Et2NH was added dropwise, within
5 h, followed by reflux for 2 h. On the next day a precipitate
of Et2NH·HCl was filtered off (under nitrogen) and washed
three times with ether. After removal of ether, the liquid resi-
1
(Si-Cl). H NMR (80 MHz, CCl4, δ (ppm)): 0.79 (s, 3H,
CH3-Si), 1.21 (t, J = 6.4 Hz, 6H, CH3-C), 3.08 (q, J =
6.4 Hz, 4H, CH2-N), 7.47–7.65 (m, 3H (Ph, m-, p-)), 7.8–8.0
(m, C-H (Ph, o-)). 13C NMR (300 MHz, CDCl3, δ (ppm)):
1.63 CH3-Si, 15.12 CH3-C, 39.37 CH2-N, 128.06, 130.06,
134.32, 135.14 (Ph). Anal. calcd. (%): C 57.99, H 7.96, N
6.14, Cl 15.56; found (%): C 57.59, 57.59, H 8.02, 8.14, N
5.83, 5.63, Cl 15.16, 15.38.
due was distilled to give 130.2
g (79% yield) of
Et2NSiMePhCl (bp 108–110°C/5 mmHg).
Preparation of (diethylamino)methylphenylsilane
Into a 0.5 L three-neck flask, fitted with a condenser and a
mechanical stirrer, was placed 5.50 g (0.145 mol) of LiAlH4
and 90 mL of dry THF. 65.8 g (0.289 mol) of (diethyl-
amino)methylphenylchlorosilane in 70 mL of dry THF was
added dropwise, within 30 min. The reaction mixture was
refluxed for 4 h, and cooled to room temperature. Solids
were filtered off and washed with dry pentane (3 × 30 mL).
Solvents were removed and the residue fractionally distilled
Et2NSiMePh(H)
Boiling point 115–117°C/21 mmHg, 86–89°C/5 Tr. nD20
1.4969. IR (neat (cm–1)): 3067, 1800–2000, 1591 (Ph), 1428
(Si-Ph), 1252 (Si- CH3), 2965, 2927, 2864 (C-H aliphat.),
2126, 2085 (Si-H), 1211, 1180, 1065 (C-N), 1028, 931 (Si-
1
N), 1030, 930 (Si-N). H NMR (80 MHz, CCl4, δ (ppm)):
0.33 (d, J = 3.2 Hz, 3H, CH3-Si), 0.94 (t, J = 7 Hz, 6H,
CH3-C), 2.82 (q, J = 7 Hz, 4H, CH2-N), 4.80 (q, J = 3.2 Hz,
1H, Si-H), 7.25 (m, 3H (Ph, m-, p-)), 7.50 (m, C-H (Ph, o-)).
Anal. calcd. (%): C 68.33, H 9.90, N 7.24; found (%): C
67.63, 67.56, H 9.86, 9.89, N 6.67, 6.83.
to give 7.5 g of MePhSiH2 (bp 25–26°C/5 mmHg; nD20
=
1.5051 (Lit. (38) value: 1.5058) and 52.2 g (58% yield) of
Et2NSiMePhH (bp 87–90°C/5 mmHg).
Reaction of (diethylamino)methylphenylsilane with
dimethyldichlorosilane
HMePhSiCl
Into a 250 mL two-neck flask was added 13.75 g (0.071
mol) of (diethylamino)methylphenylsilane. 17 mL (0.140
mol) of Me2SiCl2 was added dropwise at ~30°C. Reaction
mixture was heated to reflux and then fractionally distilled
through a Vigreux column. Four fractions were collected and
Boiling point 174–176°C, bp 92–95°C/65 mmHg. n2D0 1.5073.
IR (neat (cm–1)): 2170 (Si-H). H NMR (80 MHz, CDCl3, δ
(ppm)): 0.65 (d, J = 3.4 Hz, 3H, CH3-Si), 5.25 (q, J =
3.4 Hz, 1H, Si-H), 7.35 (m (t), 3H, Ph (m-, p-), 7.55 (m (d),
2H, Ph (o-)).
1
1
analyzed by means of H NMR (and IR): (1) bp 69–72°C
(11.5 g, Me2SiCl2); (2) bp 82–86°C/63 mmHg (4.9 g, ~95%
of Et2NSiMe2Cl and ~5% of HMePhSiCl); (3) bp 97–
115°C/65 mmHg (7.2 g, 35% of Et2NSiMe2Cl and 65% of
HMePhSiCl); (4) bp 130–140°C/64 mmHg (7.0 g, 70% of
Et2NSiMePhH (conversion 64.4%)); and 30% of
HMePhSiCl). Contents of the above fractions are based on
[(CH2)4N]2SiMe2
1
Boiling point 107–110°C/15 mmHg. n2D0 1.4682. H NMR
(80 MHz, CCl4, δ (ppm)): 0.24 (s, 6H, (CH3)2Si), 1.46 (m,
4H, (CH2)2), 2.73 (m, 4H, (CH2)2N). 13C NMR (300 MHz,
CDCl3, δ (ppm)): –3.33 CH3-Si, 26.61 (CH2)2, 46.73
(CH2)2N. Anal. calcd. (%): C 60.54, H 11.18, N 14.12, Si
14.16; found (%): C 60.63, 60.71, H11.31, 11.31, N 13.54,
13.54, Si 14.10.
1
integrations of their H NMR spectra (80 MHz, in CCl4).
Analytical data for the products
(CH2)4NSiMe2Cl
Boiling point 80–81°C/40 mmHg, 60–62°C/15 mmHg.
HMe2SiCl
1
Boiling point 36.0°C. IR (neat (cm–1)): 2170 (Si-H). H
n20D 1.4533. 1H NMR (80 MHz, δ (ppm)) in CCl4: 0.44 (s,
NMR (80 MHz, δ (ppm)), in CDCl3): 0.50 (d, 6H, (CH3)2Si),
© 2000 NRC Canada