REACTION OF ALLYLAMINE WITH HEXYLSILANE
223
+
+
2
50 C, and the column was linearly heated from 50
Me] (5), 196 [M C H ] (26), 141 [Si(NHCH
6
13
2
1
+
+.
to 250 C at a rate of 15 deg min .
CH=CH ) ] (100); IVa, 395 [M] (5), 366 [M
2
3
+
.
+
CH N] (5), 354 [M
All] (10), 339 [M
3
Hexyltrichlorosilane. Trichlorosilane (96.6 g) and
hexene (50.2 g) were mixed, and seven drops of
Speier’s catalyst (one drop = 0.017 0.18 ml) were
added to 1/3 of the mixture. The remaining mixture
was added dropwise at 75 C over a period of 1 h.
Within 3 h, the mixture warmed up from 85 to 110 C.
The mixture was distilled at atmospheric pressure.
A 10-g portion of low-boiling compounds was dis-
tilled off at 100 C/750 mm Hg. The vaccum distilla-
tion yielded two fractions (bp 92 C/38 mm Hg): first
fraction, 3 g (98% hexyltrichlorosilane), and second
fraction, 117 g (100% hexyltrichlorosilane). Yield of
+
+
C H N] (10), 310 [M C H ] (100), 268 [310
3
6
6
13
+.
+
+
C H N] (23); IVb, 395 [M] (8), 366 [M CH3]
2
4
+
+
(
6), 354 [M All] (16), 339 [M C H N] (14), 310
3 6
+
+
[M
C H ] (100), 268 [310 C H N] (26); IVc,
6 13 2 4
+.
+.
3
95 [M] (16), 366 [M
CH N] (6), 354 [M
3
+
+
+
All] (2), 339 [M C H N] (18), 310 [M C H ]
3
6
6
13
+
+.
(
3
100), 268 [310 C H N] (26); IVd, 395 [M] (31),
66 [M CH N] (14), 354 [M All] (22), 339
2 4
+.
+
3
+
+
[M
C H N] (50), 310 [M C H ] (100), 255
3 6 6 13
+
+.
[
310 C H N] (5); IVe, 395 [M] (5), 339 [M
3
5
+
+
C H N] (100), 310 [M
C H ] (46), 297 [M
3
6
6 13
+
+.
+
2
0
98] (16); IVf, 452 [M] (7), 394 [M 58] (60), 367
hexyltrichlorosilane 91%, n 1.4433 (published data
+
+
D
2
0
[M 85] (41), 337 [M 58 57] (72), 310 [M
[10]: bp 87 89 C/30 mm Hg, n 1.4435).
+
D
56
57] (100), 297 (14), 268 (10), 255 (46); IVg,
+
.
+
Hexylsilane. A 7.3-g portion of lithium aluminum
450 [M] (3), 394 [M
C H N] (42), 364 [M
3 6
+
+
+
hydride was dissolved in 200 ml of diethyl ether at
6 C over a period of 2 h. Then 50 g of hexyltrichlo-
rosilane was added dropwise with stirring at 17
8.5 C over a period of 50 min. Within 5 min after
86] (25), 337 [M 56 57] (100), 308 [M 142]
+
+.
3
(76), 268 [M 182] (12); V, 450 [M] (4), 394 [M
+
+
C H N] (55), 352 [M 57 41] (100), 323 [M
3
6
+
2
C H N 2Me] (97), 310 (25), 266 (50), 213 (18);
3 6
.
+
+
starting the addition of hexyltrichlorosilane, the mix-
ture began to warm up, and the addition was contin-
ued with cooling. The mixture was stirred for 35 min;
in so doing, its temperature decreased to 18 C, and
LiCl precipitated. The transparent solution was trans-
ferred into a separating funnel in which it was allowed
to separate into two phases. The lower layer (150 ml),
a solution of aluminum trichloride in diethyl ether,
was discarded. The upper layer (62 ml) contained
VI, 398 [M] (14), 369 [M Et] (100), 352 [M
+
+
57 41] (42), 339 (14), 300 [M 57 All] (52),
+
268 [M C H N 2Me] (50), 255 (56); VIIa, 395
3
6
+
.
+.
+
[M] (14), 366 [M CH N] (7), 354 [M All]
3
+
+
(2), 339 [M C H N] (18), 310 [M C H ] (68),
297 [M 98] (28), 268 [310 C H N] (100), 251
(22), 213 (42), 129 (30); VIIb, 395 [M] (12), 366
[M CH N] (7), 354 [M All] (10), 339 [M
3
6
6
13
+
+
2
4
+
.
+
.
+
3
+
+
+
C H N] (18), 310 [M C H ] (70), 297 [M 98]
3
6
6
13
+
hexylsilane, diethyl ether, and a part of AlCl . The
(30), 268 [310 C H N] (100), 251 (20), 213 (28),
2 4
.
3
+
+
ether was distilled off, and the residue was distilled in
a vacuum. The fraction obtained (21.87 g) consisted
of 89.6% hexylsilane, 0.6% hexyltrichlorosilane, and
129 (25); VIIc, 395 [M] (10), 310 [M C H ]
6 13
+
+
(60), 297 [M 98] (18), 268 [310 C H N] (100),
251 (20), 213 (30), 129 (18); VIId, 395 [M] (4), 339
2
4
+
+
+
9
.8% diethyl ether. Yield of hexylsilane 74%. The
[M
C H N] (12), 310 [M
C H ] (25), 297
3
6
6 13
+
+
product was washed with water to remove traces of
unchanged hexyltrichlorosilane, dried over zeolite A,
[M 98] (65), 268 [310 C H N] (100), 213 (26),
129 (26); VIIIa VIIIc, 480 [M] (1), 422 [M
2
4
+
.
2
0
+
and distilled; bp 116 118 C/750 mm Hg, nD 1.4133
C H N] (100).
2
6
published data [2]: bp 112 113 C/761 mm Hg, n2
0
D
(
c. Two drops of complex II were added to 2.3 g of
1
.4131).
Reaction of allylamine with hexylsilane. a. A
allylamine, and, after a certain period, 1.4 g of hexyl-
silane was added. The mixture was refluxed for 5 h at
62 C and left to cool; in so doing, the mixture poly-
merized. Found, %: C 63.76, 63.38; H 11.42, 11.49;
Si 13.66 13.42. C H N Si. Calculated, %: C 63.7;
mixture of 2.3 g of allylamine, 1.4 g of hexylsilane,
and three drops of Speier’s catalyst was refluxed until
a constant temperature (or 120 C) was attained.
1
2
26
2
H 11.5; Si 12.4. In a similar experiment, excess allyl-
amine was distilled off after heating. The residue also
polymerized on standing. Found, %: C 63.40, 63.57;
H 11.40, 11.50; Si 13.70, 13.50. C H NSi. Calcu-
b. Three drops of Speier’s catalyst and three drops
of an additive (vinyltriethoxysilane, allyl glycidyl
ether) were heated for 20 30 min at 50 70 C. Then
9
21
2
.3 g of allylamine and 1.4 g of hexylsilane were
lated, %: C 63.16; H 12.28; Si 16.37.
added. The mixture was refluxed until a constant
temperature (or 120 C) was attained. The low-boiling
components were distilled off, and the residue was
analyzed by GC MS. Mass spectra of the compounds
d. Two drops of catalyst II were mixed with 2.3 g
of allylamine. The mixture was heated to reflux, and
1.4 g of hexylsilane was added over a period of
30 min. The mixture was refluxed for 18.5 h and then
+
.
obtained, m/z (I , %): III, 281 [M] (12), 266 [M
rel
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 2 2006