ACYL IODIDES IN ORGANIC SYNTHESIS: IX.
505
obtained under similar conditions from 10.62 g
(0.062 mol) of acetyl iodide and 2.97 g (0.016 mol) of
tetraethoxysilane gave a fraction with bp 72–77°C,
which contained (GLC) 64% of ethyl iodide and 32%
of ethyl acetate. The still residue was silicon dioxide.
Calculated, %: Si 46.66. SiO2. Found, %: Si 44.04.
Reaction of acetyl iodide with tetramethyl(di-
vinyl)disiloxane at a ratio of 2:1. A mixture of 8.5 g
(0.05 mol) of acetyl iodide and 4.6 g (0.025 mol) of
tetramethyl(divinyl)disiloxane was heated for 7 h
under reflux. Distillation of the mixture gave 2.1 g
(84%) of acetic anhydride (identified by GLC),
bp 138–139°C; published data [27]: bp 140°C.
Reaction of acetyl iodide with 1-ethoxysilatrane.
Acetyl iodide, 2.9 g (0.017 mol), was added dropwise
to a solution of 3.73 g (0.017 mol) of 1-ethoxysilatrane
in 50 ml of toluene. The mixture spontaneously
warmed up to 40°C and was left to stand for 24 h at
room temperature. The precipitate was filtered off and
recrystallized from methylene chloride–heptane (1:1).
Yield of 2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3]un-
decan-1-yl acetate 2.52 g (63%), mp 170–171°C; pub-
lished data [19]: mp 173–174°C. According to the
GLC data, the filtrate contained ethyl iodide.
Reaction of acetyl iodide with octamethyltri-
siloxane. A mixture of 3.69 g (0.02 mol) of acetyl
iodide and 5.13 g (0.02 mol) of octamethyltrisiloxane
was heated for 6 h at 105–110°C. Distillation of the
mixture gave 3.2 g (74%) of iodotrimethylsilane,
bp 101–103°C (published data [2]: bp 106°C) and
3.9 g (87%) of dimethyl(trimethylsiloxy)silyl acetate,
bp 170–172°C, nD20 = 1.3900. IR spectrum, ν, cm–1:
1
3070 (C–H), 1710 (C=O), 1050 (SiOSi). H NMR
spectrum, δ, ppm: 2.05 (MeCO), 0.09–0.02 (Me2Si).
29Si NMR spectrum, δSi, ppm: 6.95 (Me3Si), 21.6
(Me2Si). Found, %: C 39.06; H 9.51; Si 28.34.
C7H15Si2O3. Calculated, %: C 40.74; H 8.79; Si 27.21.
Reaction of benzoyl iodide with 1-ethoxysila-
trane. Benzoyl iodide, 2.32 g (0.01 mol), was added
dropwise to a solution of 2.19 g (0.01 mol) of 1-eth-
oxysilatrane in 50 ml of toluene under stirring at room
temperature. The mixture was kept for 24 h at room
temperature, and the precipitate was filtered off and
recrystallized from xylene. Yield of 2,8,9-trioxa-5-aza-
1-silabicyclo[3.3.3]undecan-1-yl benzoate 2.23 g
(76.4%), mp 220–222°C; published data [19]: mp 221–
222°C. The filtrate contained ethyl iodide (GLC).
Reaction of acetyl iodide with octamethylcyclo-
tetrasiloxane. A mixture of 5.31 g (0.031 mol) of
acetyl iodide and 9.18 g (0.031 mol) of octamethyl-
cyclotetrasiloxane was heated for 3 h at 90°C. Dis-
tillation of the mixture gave 11.62 g (54%) of hexa-
decamethyloctasiloxane-1,8-diyl diacetate, bp 92–
95°C (10 mm). IR spectrum, ν, cm–1: 3040 (C–H),
1715 (C=O), 1250 (SiMe2), 1000–1080 (Si–O–Si),
Reaction of acetyl iodide with hexaethyldi-
siloxane. A mixture of 5.31 g (0.031 mol) of acetyl
iodide and 7.63 g (0.031 mol) of hexaethyldisiloxane
was heated for 6 h at 90°C. Distillation of the mixture
gave a fraction with bp 80–85°C (20 mm), which
contained (according to the 29Si NMR data) 40% of
triethyliodosilane and 50% of triethylsilyl acetate.
29Si NMR spectrum, δSi, ppm: 25.09 (Et3SiO), 13.01
(Et3SiI).
1
800 (SiMe2). H NMR spectrum, δ, ppm: 2.06 s (6H,
MeCO), 0.27 s (48H, SiMe2). 29Si NMR spectrum:
δSi –21.5 ppm. Mass spectrum, m/z (Irel, %): 43 (8)
[MeCO]+, 59 (8) [MeCOO]+, 73 (100) [Me2SiO]+, 267
(51) [MeCOOSiMe2OSiMe2OSiMeO]+, 355 (67) [M –
Me2SiOSiMe2OSiMe2OSiMe2COOMeO]+. Found, %:
C 34.47; H 7.91; Si 35.79. C20H54O11Si8. Calculated,
%: C 35.40; H 7.96; Si 33.00.
This study was performed under financial support
by the Council for Grants at the President of the
Russian Federation (project no. NSh-4575.2006.3).
Reaction of acetyl iodide with tetramethyl(di-
vinyl)disiloxane at a ratio of 1:1. A mixture of 8.5 g
(0.05 mol) of acetyl iodide and 9.3 g (0.05 mol) of
tetramethyl(divinyl)disiloxane was heated for 3.5 h at
60–65°C and for 3.5 h at 105–110°C. Distillation of
the mixture gave 5.8 g (55%) of dimethyl(vinyl)silyl
acetate, bp 145–150°C, nD20 = 1.4100. IR spectrum, ν,
REFERENCES
1. Voronkov, M.G. and Basenko, S.V., Sov. Sci. Rev., 1990,
vol. 15, p. 1.
1
cm–1: 3050 (C–H), 1710 (C=O). H NMR spectrum,
2. Voronkov, M.G. and Khudobin, A.Yu., Izv. Akad. Nauk
SSSR, Otd. Khim. Nauk, 1956, no. 6, p. 713.
δ, ppm: 1.9 s (3H, MeCO), –0.016 s (6H, Me2Si),
5.59 d.d and 5.78 d.d (2H, CH2=), 5.96 d.d (1H, CH=).
29Si NMR spectrum: δSi 9.8 ppm. Found, %: C 49.71;
H 8.38; Si 20.08. C6H12SiO2. Calculated, %: C 49.96;
H 8.39; Si 19.47.
3. Voronkov, M.G., Pavlov, S.F., and Dubinskaya, E.I., Izv.
Akad. Nauk SSSR, Ser. Khim., 1975, no. 3, p. 657.
4. Voronkov, M.G., Pavlov, S.F., and Dubinskaya, E.I.,
Dokl. Akad. Nauk SSSR, 1976, vol. 227, p. 607.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 4 2007