Unusual O-Csp2 Bond Cleavage in Vinyl Ethers with Organylhalosilanes [1]

Full text of DOI:10.1023/A:1024986726314

Russian Journal of General Chemistry, Vol. 73, No. 3, 2003, pp. 488 489. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 3, 2003,
pp. 521 522.
Original Russian Text Copyright
2003 by Basenko, Boyarkina, Voronkov.
LETTERS
TO THE EDITOR
2
Unusual O C
Bond Cleavage
sp
in Vinyl Ethers with Organylhalosilanes
S. V. Basenko, E. V. Boyarkina, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received June 4, 2002
2
We found a previously unknown reaction of O Csp
bond cleavage in vinyl ethers with organylhalo-
silanes, involving substitution of the halogen atom by
an alkoxy group.
H 5.47; Cl 28.50; Si 11.34. C10H14Cl2OSi. Calculated,
%: C 48.20; H 5.66; Cl 28.45; Si 11.27. The vinyl
chloride formed in the course of the reaction was
condensed in a liquid nitrogen trap and then bromi-
nated to obtain 1,2-chlorodibromoethane, bp 60 C
(8 mm), n2D0 1.5535 {published data [2]: bp 44 C
(4 mm), n2D0 1.5540}.
CH2=CHOR + XnSiR4
n
CH2=CHX + Xn 1(RO)SiR 4
,
n
R = Bu; R = CH2Cl, Me, Ph; X = F, Cl; n = 2 4.
The reactions of trichloro(phenyl)silane with butyl
vinyl silane at 1:2 and 1:3 molar ratios, as well as
the reactions of butyl vinyl ether with PhMeSiCl2,
ClCH2SiCl3, MeSiCl3, SiCl4, and PhSiF3 were per-
formed in a similar way.
For example, the reaction of butyl vinyl ether with
trichloro(phenyl)silane at a 1:1 molar ratio at 20 C
gives vinyl chloride and dichloro(butoxy)phenylsilane
in a near-quantitative yield (96%). At 2:1 and 3:1
reagent molar ratios, a mixture of chloro(butoxy)-
phenylsilanes PhSi(OBu)3 nCln (n = 0 2) is formed.
The major component of the mixture is dichloro(but-
oxy)phenylsilane.
Dichloro(chloromethyl)butoxysilane, bp 58 C
1
(3 mm), n2D0 1.4412, d240 1.1560. IR spectrum, cm :
The reactions of butyl vinyl ether with ClCH2SiCl3,
PhMeSiCl2, MeSiCl3, and SiCl4 at 1:1 molar ratios at
20 C, too, give chloro(butoxy)(methyl)phenylsilane,
dichloro(chloromethyl)butoxysilane, dichloro(butoxy)-
methylsilane, and trichloro(butoxy)silane (yields 32,
57, 45, and 37%, respectively). From butyl vinyl ether
and trifluoro(phenyl)silane under similar conditions
we obtained difluoro(butoxy)phenylsilane in an yield
of up to 10% and poly(butyl vinyl ether).
460, 570 [ (Si Cl)], 1090 [ (Si O)], 1385, 1460
1
[ (CH2)], 2870, 2930, 2950 [ (CH)]. H NMR spec-
trum, , ppm : 0.93 t (CH3CH2), 1.39 m (CH3CH2),
1.63 m (CH2CH2CH2), 3.08 (ClCH2), 3.98 t (OCH2).
Found, %: C 27.19; H 5.07; Cl 48.25; Si 7.34;
C5H11Cl3OSi. Calculated, %: C 27.10; H 5.00; Cl
48.00; Si 7.22.
Reaction of butyl vinyl ether with trichloro-
(phenyl)silane. A mixture of 10.0 g of butyl vinyl
ether and 21.2 g of trichloro(phenyl)silane was al-
lowed to stand at room temperature for 1 day. Vacuum
distillation gave 23.9 g (96%) of dichloro(butoxy)-
phenylsilane, bp 110 C (3 mm), n2D0 1.4930, d420
1.1246 {published data [1]: bp 130 135 C (14 mm)}.
Dichloro(butoxy)(methyl)phenylsilane, bp 87 C
(2 mm), n2D0 1.4845 {published data [3]: bp 101 C
(5 mm), n2D0 1.4838}.
Dichloro(butoxy)methylsilane, bp 46 C (15 mm),
n2D0 1.4130 {published data [4]: bp 29.5 C (9 mm),
n2D0 1.4125}.
1
IR spectrum, , cm : 460, 560 (Si Cl), 1080, 1115
(Si O), 1430 (Si Ph), 1590 (C=C), 2870, 2950 (CH3),
3050, 3070 (CH2). 1H NMR spectrum, , ppm: 0.93 t
(CH3CH2), 1.40 m (CH3CH2), 1.65 m (CH2CH2CH2),
4.00 t (OCH2), 7.2 7.8 m (C6H5). Found, %: C 48.39;
Trichloro(butoxy)silane, bp 45 C (15 mm), nD20
1070-3632/03/7303-0488$25.00 2003 MAIK Nauka/Interperiodica

2
UNUSUAL O Csp BOND CLEAVAGE
489
1.4120 {published data [5]: bp 38 C (10 mm), nD20
1.4118}.
Bruker DPX-400 instrument (400 MHz) for 15 20%
solutions in CDCl3 and C6D6, internal reference
HMDS.
Difluoro(butoxy)phenylsilane, bp 85 C (10 mm).
IR spectrum, , cm : 860, 955 (Si F), 1090, 1145
1
REFERENCES
(Si O), 1435 (Si Ph), 1595 (C=C), 2875, 2940, 2960
(CH3), 3050, 3080 (CH2). 1H NMR spectrum, , ppm:
0.88 t (CH3CH2), 1.35 m (CH3CH2), 1.50 m (CH2CH2
CH2), 3.40 t (OCH2), 7.2 7.5 m (C6H5).
1. Bazant, V. and Benes, J., Collect. Czech. Chem.
Commun., 1959, vol. 24, no. 2, p. 624.
2. Bachman, G.B., Logan, T.J., Hill, K.R., and Stan-
dish, N.W., J. Org. Chem., 1960, vol. 25, no. 8, p. 1312.
1
Poly(butyl vinyl ether). H NMR spectrum,
,
3. Chappelow, C.C., Jr., Elliott, R.L., and Goodwin J.T.,
ppm: 1.02 (CH3CH2), 1.40 1.60 (CH3CH2), 1.65
Jr., J. Chem. Eng. Data, 1963, vol. 8, no. 1, p. 82.
2.30 (CH2CH2CH2, OCHCH2), 3.40 4.00 (OCH2,
OCH). Found, %: C 71.86; H 12.20. C6H12O. Cal-
culated, %: C 71.95; H 12.08.
4. Shostakovskii, M.F., Sokolov, B.A., Dmitrieva, G.V.,
and Alekseeva, G.M., Zh. Obshch. Khim., 1964, vol. 34,
no. 9, p. 2839.
The IR spectra were obtained on a Specord IR-75
instrument. The H NMR spectra were measured on a
5. Currell, B.R., Frazer, M.J., Haines, E., and Leader, L.,
1
J. Inorg. Nucl. Chem., 1959, vol. 12, no. 1 2, p. 45.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 3 2003