ELECTROPHILIC CYCLIZATION OF DIMETHYL( -PHENYLAMINOALKYL)ALKENYLSILANES
1877
3
3
3
To a 0.68-g portion of this fraction dissolved in
2 ml of ether a solution of 0.4 ml of acetylchloride in
1.5 ml of ether was added and after 15-min stirring
the mixture was hydrolyzed with water. To the water
layer was added 10% solution of NaOH to alkaline
reaction and it was extracted with ether. Organic
phase was dried over Na2SO4. After removing of ether
in a rotor evaporator 0.15 g of compound II was iso-
lated by column chromatography (hexane ether, 9:1
C6H5, J 8.0 Hz), 7.23 d.d (2Hm, C6H5, J 8.0, J
7.2 Hz). 13C NMR spectrum, C, ppm: 1.83 (CH3Si),
15.36 (SiCCN), 15.56 (SiCCC), 23.37 (CCC), 47.93
(SiCCN), 54.15 (CCCN), 110.85 (Co), 114.98 (Cp),
129.30 (Cm), 147.61 (Ci). 29Si NMR spectrum,
ppm: 5.4. Found, %: N 6.07; Si 12.84. C13H21NSi.
Calculated, %: N 6.38; Si 12.80.
,
Si
1-Phenyl 2,3,3-trimethyl-3-silapiperidine (IX)
was isolated from water layer after treatment of the
reaction mixture with acetyl chloride. Yield 13%, Rf
1:1), Rf 0.73 (hexane ether, 9 :1), n2D4 1.5174. H
1
NMR spectrum, , ppm: 0.25 s (6H, Me2Si), 1.03 t
(2H, SiCH2C), 2.52 s (2H, SiCH2N), 3.44 t (2H,
0.71, n2D0 1.5162. H NMR spectrum, , ppm: 0.07 s
1
3
4
(3H, MeSi), 0.15 s (3H, MeSi), 0.73 m (2H, SiCH2C),
1.17 d (3H, CH3, 3J 7.5 Hz), 1.80 m (1Hax, CCH2C),
1.90 m (1Heq, CCH2C), 3.06 q.d (1Hax, CCH2N, JAB
CCH2N), 6.68 t.t (1Hp, C6H5, J 7.4, J 1.0 Hz),
6.80 d (2Ho, C6H5, J 8.0 Hz), 7.23 d.d (2Hm, C6H5, 3J
3
8.0, J 7.4 Hz). These data are identical with the
3
3
14.1, JH
11.2, JH
2.2 Hz), 3.30 q (1H, CH,
earlier published ones [15]. 13C NMR spectrum,
,
Hax
Heq
a
ax
x
C
3
ppm: 2.67 (CH3Si), 12.54 (SiCC); 37.16 (SiCN),
48.06 (CCN), 113.06 (Co), 116.148 (Cp), 128.947
(Cm), 151.19 (Ci). 29Si NMR spectrum, Si, ppm:
16.54.
J 7.5 Hz), 3.42 d.t (1Heq, CCH2N, 2JAB 14.1, JH
Hax
eq
3
3
2.2, JH
2.2 Hz), 6.65 t (1Hp, C6H5, J 7.2 Hz),
Heq
eq
3
6.84 d (2Ho, C6H5, J 8.5 Hz), 7.18 d.d (2Hm, C6H5,
3J 7.2, 3J 8.5 Hz). 13C NMR spectrum, C, ppm: 3.66
(CH3Si), 3.84 (CH3Si), 10.08 (SiCC), 11.39 (CH3),
23.72 (CCC), 43.03 (CH), 45.76 (CH2N), 114.75 (Co),
116.58 (Cp), 129.04 (Cm), 147.64 (Ci). Found, %:
Similarly, from amines III, V, VII, and X were
prepared heterocyclic compounds IV, VI, VIII, IX,
and XI, respectively.
1-Phenyl-3,3,5-trimethyl-3-silapyrrolidine (IV).
Yield 92%, Rf 0.73 (hexane ether, 9:1), n2D0 1.5170.
1H NMR spectrum, , ppm: 0.22 s (3H, MeSi), 0.33 s
(3H, MeSi), 0.81 d (1H, SiCH2C, JAB 14.5 Hz), 0.99 d
(3H, CH3, 3J 6.4 Hz), 1.19 d.d (1H, SiCH2C, JAB 14.5,
3J 8.5 Hz), 2.31 d (1H, SiCH2N, JAB 13.3 Hz), 2.66 d
N 6.67; Si 12.62. C13H21NSi. Calculated, %: N 6.38;
Si 12.80.
1-Phenyl 2,4,4-trimethyl-4-silapiperidine (XI).
1
Yield 30%, Rf 0.69. H MMR spectrum, , ppm:
0.07 s (3H, MeSi), 0.17 s (3H, MeSi), 0.69 d.t (1Hax,
SiCH2C, 2J 14.4, 3JH
3.6, 3JH
3.2 Hz),
3
Hax
2
Hax
ax
eq
(1H, SiCH2N, JAB 13.3 Hz), 4.51 d.q (1H, CH, J 8.5,
3
3J 6.4 Hz,), 6.64 t (1Hp, C6H5, 3J 5.2 Hz), 6.79 d (2Ho,
0.77 d.d (1Hax, SiCH2C, J 14.7, JH
7.0 Hz),
Hax
eq
3
3
3
1.11 1.19 m (2Heq, SiCH2CN and SiCH2C), 1.32 d
C6H5, J 8.2 Hz), 7.20 d.d (2Hm, C6H5, J 8.2, J
(3H, CH3, 3J 6.5 Hz), 3.43 q.d (1Hax, CH2N, 2J 14.9,
5.2 Hz). This corresponds to the published data [15].
3JH
2J 14.9, JH
12.9, 3JH
3.6 Hz), 3.74 q.d (1Heq, CH2N,
Hax
Heq
ax
ax
1-Phenyl-4,4-dimethyl-4-silapiperidine (VI).
3
3
1
6.5, JH
2.7 Hz), 4.15 q (1H,
Heq
Heq
Yield 3%, Rf 0.79 (hexane ether, 9:1). H MMR
ax
eq
4
spectrum, , ppm: 0.09 s (6H, Me2Si), 0.81 m (4H,
CH, J 6.5 Hz), 6.73 t.t (1Hp, C6H5, 3J 8.3, J 1.0 Hz),
3
3
SiCH2C), 3.86 m (4H, CH2N), 6.70 t (1Hp, C6H5, J
6.82 d (2Ho, C6H5, J 8.1 Hz), 7.23 d.d (2Hm, C6H5,
5.2 Hz), 6.88 d (2Ho, C6H5, 3J 8.1 Hz), 7.24 d.d (2Hm,
3
3J 8.3, J 8.1 Hz). Found, %: N 6.99; Si 12.80.
3
C6H5, 3J 8.1, J 5.2 Hz). Mass spectrum, m/z (Irel, %):
C13H21NSi. Calculated, %: N 6.38; Si 12.80.
205 (60) [M]+, 176 (33), 162 (12), 149 (100)
[Me2SiNC6H5]+, 134 (9), 119 (12), 104 (12), 91 (5),
77 (23), 59 (9). Found, %: N 6.41; Si 13.39.
C12H19NSi. Calculated, %: N 6.82; Si 13.68.
1,2-Bis(2-phenylaminoethyl)-1,1,2,2-tetramethyl-
disiloxane (XIV) was isolated in 26% yield, Rf 0
(hexane ether, 9:1). 1H NMR spectrum, , ppm:
0.14 s (6H, Me2Si), 0.96 m (2H, SiCH2), 3.18 m (2H,
CH2N), 6.60 m (2Ho, C6H5), 6.71 t (1Hp, C6H5),
7.15 m (2Hm, C6H5). 13C NMR spectrum, C, ppm:
0.76 (MeSi), 19.37 (SiCH2), 39.78 (CH2N), 113.09
(Co, C6H5), 117.58 (Cp, C6H5), 129.32 (Cm, C6H5),
148.22 (Ci, C6H5). 29Si NMR spectrum, Si, ppm: 6.87.
Mass spectrum, m/z (Irel, %): 372 (20) [M]+, 253 (15),
224 (55), 208 (100), 177 (15), 147 (22), 131 (26), 106
(86), 77 (22), 65 (11). Found, %: N 7.44; Si 15.36.
C20H32N2OSi2. Calculated, %: N 7.52; Si 15.07.
1-Phenyl-4,4-dimethyl-4-silaazepane (VIII) was
isolated from ethereal layer after treatment of reaction
mixture with acetyl chloride. Yield 36%, Rf 0.73
(hexane ether, 9:1), n2D3 1.5180. 1H NMR spectrum, ,
ppm: 0.11 s (6H, Me2Si), 0.76 (A part of AA XX
3
spectrum, 2H, SiCH2CN), 1.13 t (2H, SiCH2CC, J
6.9 Hz), 1.84 m (2H, CCH2C), 3.46 (X part AA XX
3
spectrum, 2H, SiCCH2N), 3.60 t (2H, FCCCH2N, J
3
6.9 Hz), 6.64 t (1Hp, C6H5, J 7.2 Hz), 6.67 d (2Ho,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 12 2001