ACYL IODIDES IN ORGANIC SYNTHESIS.
149
bp 280–282°C, 102°C (2 mm); 3.79 g (81%, calculated
on the reacted amine) of triethyl(iodo)germane (IVa),
bp 53–55°C (2 mm); published data [9]: bp 212.3°C.
1H NMR spectrum, δ, ppm: 1.12 t (9H, CH3, J =
7.7 Hz), 1.30 q (6H, CH2, J = 7.7 Hz). 13C NMR spec-
trum, δC, ppm: 9.63 (CH3), 11.15 (CH2); and 2.2 g
(66%, calculated on the reacted amine) of N,N-bis(tri-
methylsilyl)acetamide (IIIa), bp 159°C; published data
N-Ethyl-N-trimethylsilylbenzamide (IId). Ben-
zoyl iodide, 6.96 g (30 mmol), was added dropwise at
room temperature to 5.68 g (30 mmol) of N,N-bis(tri-
methylsilyl)ethanamine, and the mixture was stirred
for 13 h at 80–104°C. The precipitate of (Me3Si)2NEt·
1
IC(O)Ph, 9.86 g, was filtered off. H NMR spectrum,
δ, ppm: 0.06 s (9H, CH3), 1.25 t (CH3, J = 7.0 Hz),
3.31 q (CH2, J = 7.0 Hz), ), 7.44−7.96 m (Ph).
13C NMR spectrum, δC, ppm: 1.92 (Me3Si), 14.72
(CH2CH3), 41.64 (CH2CH3); 125.92, 128.78, 132.73
(Ph); 163.04 (C=O).
1
[6]: bp 67.5°C (30 mm). H NMR spectrum, δ, ppm:
13
0.22 s (18H, CH3), 1.98 s (CH3). C NMR spectrum,
δC, ppm: 2.24 (CH3) , 27.11 (CH3), 169.92 (C=O).
The filtrate was distilled to isolate 2.16 g (36%) of
iodotrimethylsilane (I) and 1.65 g (25%) of amide IId,
bp 210–270°C; published data [8]: bp 103–104°C
Reaction of (triethylstannyl)bis(trimethylsilyl)-
amine with acetyl iodide. Acetyl iodide, 4.63 g
(27 mmol), was added dropwise to 9.97 g (27 mmol)
of (triethylstannyl)bis(trimethylsilyl)amine, and the
mixture was stirred for 10 h at 80–90°C. Distillation
gave 6.53 g (73%) of triethyl(iodo)stannane (IVb)
[bp 70–75°C (6 mm); published data [9]: bp 212.3°C.
1H NMR spectrum, δ, ppm: 1.28 t (9H, CH3, J =
7.9 Hz), 1.35 q (6H, CH2, J = 7.9 Hz). 13C NMR spec-
trum, δC, ppm: 8.71 (CH3), 11.32 (CH2)] and 3.67 g
(67%) of amide IIIa.
1
(12 mm). H NMR spectrum, δ, ppm: 0.09 s (9H,
CH3), 0.99 t (CH3, J = 6.9 Hz), 2.83 q (CH2, J =
6.9 Hz), 7.35–7.97 m (Ph). 13C NMR spectrum, δC,
ppm: 2.3 (Me3Si), 20.6 (CH2CH3), 39.4 (CH2CH3);
128.02, 130.28, 132.47 (Ph); 165.51 (C=O).
N-Phenyl-N-trimethylsilylbenzamide (IIe). Ben-
zoyl iodide, 5.46 g (24 mmol), was added dropwise to
5.59 g (24 mmol) of N,N-bis(trimethylsilyl)aniline, the
mixture was stirred for 13 h at 100–105°C, the precip-
itate was filtered off, and the filtrate was distilled
under reduced pressure to isolate 1.37 g (21%) of
amide IIe, bp 130–145°C (1 mm); published data [9]:
Reaction of (triethylgermyl)bis(trimethylsilyl)-
amine with benzoyl iodide. Benzoyl iodide, 5.04 g
(22 mmol), was added dropwise to 6.95 g (22 mmol)
of (triethylgermyl)bis(trimethylsilyl)amine, and the
mixture was stirred for 37 h at 55–65°C. Distillation
gave 3.79 g (37%) of triethyl(iodo)germane (IVa)
1
bp 106°C (0.15 mm). H NMR spectrum, δ, ppm:
13
0.29 s (9H, CH3), 7.10–7.84 m (Ph). C NMR spec-
1
[bp 45–47°C (2 mm). H NMR spectrum, δ, ppm:
trum, δC, ppm: 1.88 (Me3Si); 120.31, 133.60, 139.20
1.11 t (9H, CH3, J = 7.7 Hz), 1.31 q (6H, CH2, J =
7.7 Hz). 13C NMR spectrum, δC, ppm: 9.78 (CH3),
11.28 (CH2)] and 5.96 g of a mixture boiling at 48–
55°C (2 mm), which contained (according to the NMR
data) N,N-bis(trimethylsilyl)benzamide (IIIb) {bp 48–
(Ph); 165.44 (C=O).
Thermal decomposition of the precipitate under
reduced pressure gave an additional amount, 1.00 g
(16 %), of amide IIe. Overall yield 2.37 g (37%).
1
N,N-Bis(trimethylsilyl)benzamide (IIf). Benzoyl
iodide, 8.58 g (37 mmol), was added dropwise to
8.64 g (37 mmol) of tris(trimethylsilyl)amine, and the
mixture was stirred for 8 h at 120–130°C. Distillation
gave 4.39 g (59%) of iodotrimethylsilane (I) and
3.15 g (32%) of amide IIf, bp 98–110°C (2 mm);
49°C (0.04 mm) [10]. H NMR spectrum, δ, ppm:
13
0.40 s (18H, CH3), 7.46–8.05 m (Ph). C NMR spec-
trum, δC, ppm: 1.98 (18H, CH3), 128.27–132.89
(Ph), 166.74 (C=O)} and (Me3Si)2NC(O)Ph·IGeEt3
[1H NMR spectrum, δ, ppm: 0.18 s (18H, CH3), 1.11 t
(9H, CH3, J = 6.7 Hz), 1.29 q (6H, CH2, J = 6.7 Hz),
1
13
published data [6]: bp 48–49°C (0.04 mm). H NMR
7.39–8.03 m (Ph). C NMR spectrum, δC, ppm: –0.15
spectrum, δ, ppm: 0.40 s (18H, CH3); 7.40, 7.84,
8.56 m (Ph). 13C NMR spectrum, δC, ppm: 1.97
(Me3Si); 128.41, 132.18, 145.8 (Ph); 166.86 (C=O).
(CH3), 9.64 (CH2CH3), 11.15 (CH2CH3), 128.28–
132.90 (Ph), 194.81 (C=O)].
Reaction of (triethylstannyl)bis(trimethylsilyl)-
amine with benzoyl iodide. Benzoyl iodide, 4.63 g
(27 mmol), was added dropwise to 8.5 g (23 mmol) of
(triethylstannyl)bis(trimethylsilyl)amine, and the mix-
ture was stirred for 10 h at 80–90°C. Distillation gave
4.82 g (63%) of triethyl(iodo)stannane (IVb) [bp 48–
Reaction of (triethylgermyl)bis(trimethylsilyl)-
amine with acetyl iodide. Acetyl iodide, 3.79 g
(22 mmol), was added dropwise to 7.15 g (22 mmol)
of (triethylgermyl)bis(trimethylsilyl)amine, and the
mixture was stirred for 5 h at 80–90°C. Distillation
gave 1.91 g of the initial amine (conversion 73%);
1
49°C (2 mm). H NMR spectrum, δ, ppm: 0.94 t (9H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 1 2013