ACCEPTED MANUSCRIPT
2
.2. N-[(trimethoxysilyl)methyl]aniline (1).
A mixture of 8.53 g (50 mmol) (chloromethyl)trimethoxysilane and the excess of aniline 18.6 g
(~200 mmol) was sealed in glass ampoule. During the 20-hour ampoule was heated at
o
temperature 85 C. The ampoule was cooled to room temperature and opened and freshly
.
distilled Et O (150 mL) was added to the residue. The precipitate of PhNH HCl was filtered off,
2
2
washed by ether (35 mL x 2) and the solvent removed from the filtrate by distillation on rotary
evaporator. Compound 1 as yellowish liquid was isolated by vacuum distillation of the resulting
2
5
1
residue (yield 10.92 g, 96 %). Bp 96-99 °C/3 mm Hg, nD = 1.5054. H NMR (CD CN, δ ppm):
3
1
3
2
.54 (s, 2 H, SiCH N), 3.62 (s 9 H, OMe), 4.11 (broad s, 1 H, NH), 6.65-7.11 (m, 5H, Ph). C
2
2
9
NMR (CD CN, δ ppm): 28.20 (SiCH N), 51.78 (OMe), 113.88, 118.75, 130.46, 151.96 (Ph). Si
3
2
NMR (CD CN, δ ppm): - 47.49. Anal. Calcd. for C H NO Si: C, 52.83; H, 7.54; N, 6.16, Si,
3
10 17
3
1
2.35. Found: C, 52.69; H, 7.73; N, 6.11; Si, 12.79.
2
.3. 1-[N-Phenyl(aminomethyl)]silatrane (2).
Triethanolamine 1.49 g (10 mmol) was added dropwise to 2.27 (10 mmol) of N-
(phenylamino)methyl]trimethoxysilane at stirring vigorously. The methanol released in this
[
reaction was removed in vacuum immediately after homogenization of reaction mixture. The
white solid residue was dried in vacuum, yield is 2.69 g (93%). Colorless crystals suitable for
structural analysis were obtained by the recrystallization from benzene. M. p. with the
1
decomposition >199 °C (in a sealed capillary). H NMR (CD CN, δ ppm): 2.01 (s, 2 H,
3
3
3
SiCH N), 2.87 (t, 6 H, NCH , J = 5.9 Hz), 3.73 (t, 6 H, OCH , J = 5.9 Hz), 4.05 (broad s, 1 H,
2
2
2
13
NH), 6.50-7.03 (m, 5H, Ph). C NMR (CD CN, δ ppm): 35.05 (SiCH N), 51.88 (NCH ), 58.37
3
2
2
2
9
(
OCH ), 112.95, 116.41, 130.25, 153.22 (Ph). Si NMR (CD CN, δ ppm): - 77.47. Anal. Calcd.
2
3
for C H N O Si: C, 55.69; H, 7.19; N, 9.99, Si, 10.02. Found: C, 55.21; H, 7.06; N, 10.08; Si,
1
3
20
2
3
1
0.47.
2
.4. 1-[N-Phenyl(aminomethyl)]silatrane hydrochloride (3). The solution of HCl (0.0365 g, 1
mmol) in carefully dried benzene was added dropwise to benzene solution of compound 2 (0.280
о
g, 1 mmol) at 10 С. After 10 minutes the reaction mixture was evaporated to remove the
solvent. The solid residue was purified by the recrystallization in chloroform/benzene (5: 2). M.
1
p. with the decomposition >219 °C (in a sealed capillary). H NMR (CD CN, δ ppm): 2.42 (s, 2
3
3
3
H, SiCH N), 2.94 (t, 6 H, NCH , J = 5.9 Hz), 3.71 (t, 6 H, OCH , J = 5.9 Hz), 6.75 (broad s,
2
2
2
1
3
2
5
H, NH), 7.15-7.63 (m, 5H, Ph). C NMR (CD CN, δ ppm): 46.26 (SiCH N), 51.56 (NCH ),
3 2 2
2
9
7.87 (OCH ), 122.14, 123.80, 130.60, 146.55 (Ph). Si NMR (CD CN, δ ppm): - 84.75. Anal.
2
3
3