MIGRATION OF TRIMETHYLSILYL GROUP
1453
on a Tsvet-500 chromatograph equipped with a thermal
conductivity detector and a glass column, 3 m×4 mm
packed with 10% of PSM-1000 on Inerton Super
(trimethylsilyl)amide in 100 ml of THF. The mixture
was heated to the boiling point, a solid separated, and
the mixture was stirred for 4 h on heating under reflux.
The solvent was distilled off, and the residue was
subjected to vacuum distillation to isolate 8.50 g of
a mixture of compounds I and II at a ratio of 1:4,
bp 62–78°C (2 mm).
(
0.125–0.150 mm); carrier gas helium.
Sodium bis(trimethylsilyl)amide was prepared ac-
cording to the procedure described in [7].
Reaction of sodium bis(trimethylsilyl)amide with
bromobenzene in toluene. Bromobenzene, 42.4 g
Reaction of sodium bis(trimethylsilyl)amide with
bromobenzene in triethylamine. Triethylamine,
(
270 mmol), was added dropwise at room temperature
1
00 ml, was added to 15.1 g (82 mmol) of sodium bis-
to a solution of 49.5 g (270 mmol) of sodium bis(tri-
methylsilyl)amide in 250 ml of toluene. The mixture
was heated to the boiling point, a solid separated, and
the mixture was stirred for 4 h on heating under reflux.
The solvent was distilled off, and the residue was
subjected to vacuum distillation to isolate 25.1 g of
a mixture of compounds I and II at a ratio of 4 :1,
bp 50–65°C (1 mm).
(
trimethylsilyl)amide. The latter is moderately soluble
in triethylamine. Bromobenzene, 12.9 g (82 mmol),
was added dropwise at room temperature, and the mix-
ture was heated to the boiling point and kept boiling
for 8 h under stirring. The solvent was distilled off, and
the residue was distilled under reduced pressure to
isolate 5.5 g of N,N-diethylaniline, bp 58–60°C
(
2 mm); published data [11]: bp 217°C. The product
1
N,N-Bis(trimethylsilyl)aniline (I). H NMR spec-
was identified by GLC using an authentic sample and
1
1
trum, δ, ppm: 0.05 s (18H, Me Si), 6.88 d.d (2H, o-H,
3
by H NMR. H NMR spectrum, δ, ppm: 1.13 t (6H,
CH ), 3.32 q (4H, CH ), 6.64–7.47 m (H ).
3
4
3
4
J = 7.7, J = 1.1 Hz), 7.03 t.t (1H, p-H, J = 7.3, J =
3
2
arom
3
1
.1 Hz), 7.18 d.d (2H, m-H, J = 7.7, 7.3 Hz).
1
3
C NMR spectrum, δ , ppm: 2.09 [(CH ) Si], 123.62
C
3 3
REFERENCES
p
m
o
i
15
(
C ), 128.44 (C ), 130.23 (C ), 147.98 (C ). N NMR
2
9
spectrum: δ –334.4 ppm. Si NMR spectrum:
1. Abel, E.W. and Armitage, D.A., J. Chem. Soc., 1964,
N
p. 1528.
δ 4.5 ppm. Mass spectrum, m/z (I , %): 237 (25)
Si
rel
+
+
[
M] , 222 (100) [M – 15] , 206 (20), 150 (10)
2. Wannagat, U., Krüger, C., and Niederprüm, H.,
+
+
Z. Anorg. Allg. Chem., 1962, vol. 314, p. 80.
[
Me SiPh] , 73 (15) [Me Si] .
3
3
1
3. Klebe, J.F., Bush, J.B., Jr., and Lyons, J.E., J. Am.
N,2-Bis(trimethylsilyl)aniline (II). H NMR spec-
Chem. Soc., 1964, vol. 86, p. 4400.
trum, δ, ppm: 0.27 s [9H, (CH ) SiN], 0.31 s [9H,
3
3
3
4. Nagy, J., Hegedus-Zimonyi, E., and Hencsei, P., Magy.
Kem. Foly., 1970, vol. 76, no. 5, p. 267.
5. King, F.D. and Walton, D.R.M., J. Chem. Soc., Chem.
(
CH ) SiC], 6.71 d (1H, 6-H, J = 8.0 Hz), 6.73 d.d.d
3
3
6,5
3 3 4
(
1H, 4-H, J = 8.0, J = 7.2, J = 0.7 Hz),
4
, 3
4, 5
4, 6
3 3 4
7
1
.18 d.d.d (1H, 5-H, J = 8.0, J = 7.2, J
=
5
, 6
4, 5
5, 3
Commun., 1974, p. 256.
. Hils, J., Hagen, V., Ludwig, H., and Rühlmann, K.,
Chem. Ber., 1966, vol. 99, p. 776.
. Bailey, R.E. and West, R., J. Organomet. Chem., 1965,
vol. 4, p. 430.
. Bergstrom, F.W., Wright, R.E., Chandler, C., and
Gilbey, W.A., J. Org. Chem., 1936, vol. 1, p. 170.
3
4
.5 Hz), 7.28 d.d (1H, 3-H, J = 7.2, J = 1.5 Hz).
3
,4
5,3
6
7
8
9
1
3
C NMR spectrum, δ , ppm: –0.57 [(CH ) SiC], 0.15
C
3 3
6
4
2
[
(CH ) SiN], 115.24 (C ), 117.58 (C ), 125.09 (C ),
3
3
5
3
1
15
1
30.38 (C ), 135.30 (C ), 152.35 (C ). N NMR spec-
29
trum: δ –323.8 ppm. Si NMR spectrum, δ , ppm:
N
Si
2
.6 (NSiMe ), –6.3 (CSiMe ). Mass spectrum, m/z
3
3
+ +
(
I , %): 237 (100) [M] , 222 (80) [M – 15] , 206 (25),
64 (10), 150 (15) [Me SiPh] , 73 (80) [Me Si] .
rel
. Wittig, G. and Benz, E., Chem. Ber., 1959, vol. 92,
p. 1999.
+
+
1
3
3
Reaction of sodium bis(trimethylsilyl)amide with
bromobenzene in tetrahydrofuran. Bromobenzene,
5.5 g (98 mol), was added dropwise at room tempera-
ture to a solution of 18.1 g (98 mmol) of sodium bis-
10. Wittig, G. and Merkle, W., Chem. Ber., 1943, vol. 76,
p. 109.
1
11. Beilsteins Handbuch der organischen Chemie,
vol. H12 (3), p. 260.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 10 2013