Chloromethyl(isoproxy)diphenylsilane
Russ. Chem. Bull., Int. Ed., Vol. 66, No. 7, July, 2017
1319
Experimental
via a syringe under vigorous stirring at 5 °С. The reaction mixꢀ
ture was stirred for 10 h and kept for 16 h. The solution was
decanted and concentrated in vacuo. Vacuum distillation of the
residue afforded 4.19 g (74%) of compound 2, b.p. 153—155 °C
1H, 13C, and 29Si NMR spectra of compounds 1 and 2 were
recorded with a Bruker DPX 400 instrument (working frequenꢀ
cies of 400.13, 100.61, and 79.5 MHz, respectively) in CDCl3.
2
0
1
(
3 mm Hg), nD 1.5444. H NMR, δ: 1.27 (d, 6 H, Me СH,
2
3
3
J = 5.9 Hz); 4.43 (sept, 1 Н, Me СH, J = 5.9 Hz); 7.41—7.69
2
The chemical shifts are given in the δ scale relative to Me Si as
4
13
(
1
m, 10 Н, Ph). C NMR, δ: 25.19 (Me СH); 66.78 (Me СH);
28.00 (C ); 130.87 (C ); 134.39 (C ); 154.93 (C ). Si NMR,
m i p o
2
2
an internal standard. Commercially available dichlorodiꢀ
phenylsilane, tris(dimethylamino)phosphine, bromochloroꢀ
methane, propanꢀ2ꢀol, and urea were used. Dichlorodiphenylꢀ
silane and bromochloromethane were distilled prior to use. Proꢀ
panꢀ2ꢀol and other solvents were purified by the standard proꢀ
cedures. All syntheses were carried out under dry argon.
Synthesis of chloromethyl(isopropoxy)diphenylsilane (1). To
a solution of freshly distilled bromochloromethane (3.88 g,
2
9
δ: –10.94. Found (%): C, 64.71; H, 6.07. C H17ClOSi. Calcuꢀ
1
5
lated(%): C, 65.08; H, 6.19.
The results described in this work were obtained by
using the analytical equipment of the Baikal Center for
Collective Use of the Siberia Branch of the Russian Acadꢀ
emy of Sciences.
6
0
0
.03 mol) and chloro(isopropoxy)diphenylsilane 2 (2.77 g,
.01 mol) in benzene (50 mL), tris(dimethylamino)phosphine
(
1.63 g, 0.01 mol) was added at room temperature. The reacꢀ
References
tion mixture was stirred at room temperature for 4 h and then
refluxed for 10 h. After cooling, the solution was filtered and
treated with pentane (50 mL) to remove the quaternary phosꢀ
phonium salt. The precipitate was filtered off and the filtrate
was concentrated. Vacuum distillation of the residue afforded
1
2
.K. Yoon, D. Son, J. Organomet. Chem., 1997, 545—546, 185.
.I. Ruppert, K. Schlich, W. Volbach, Tetrahedron Lett., 1984,
2
5, 2195.
3
.G. G. Furin, Russ. J. Org. Chem., 1997, 33, 1209.
1
.83 g (63%) of compound 1, b.p. 168—170 (3 mm Hg),
2
0
1
3
4.G. K. S. Prakash, A. K. Yudin, Chem. Rev., 1997, 97, 757.
5.G. N. Koidan, A. P. Marchenko, A. M. Pinchuk, Zh. Obshch.
Khim., 1990, 60, 709 [Russ. J. Gen. Chem. (Engl. Transl.),
nD 1.5332. H NMR, δ: 1.24 (d, 6 H, Me СH, J = 6.0 Hz);
2
7
2
3
.53 (s, 2 H, СH Cl); 4.31 (sept, 1 Н, Me СH, J = 6.0 Hz );
2
2
1
3
.37—7.63 (m, 10 Н, Ph). C NMR, δ: 25.27 (Me СH); 36.99
2
1
990, 60].
(
(
СH Cl); 67.48 (Me СH); 128.06 (C ); 130.92 (C ); 134.44
2 2 m i
2
9
6.A. J. Gordon, R. A. Ford, The Chemist´s Companion.
A Handbook of Practical Data, Techniques and References, John
Wiley and Sons, New York, 1972, 537 pp.
C ); 135.02 (C ). Si NMR, δ: –16.40. Found (%): C, 65.67;
p
o
H, 6.37. C16H19ClOSi. Calculated (%): C, 66.07; H, 6.58.
Synthesis of chloro(isopropoxy)diphenylsilane (2). To a soꢀ
lution of chloro(diphenyl)silane (5.6 g, 0.02 mol) in hexane
(
75 mL), excess urea (2 g, preliminary dried) was added followꢀ
Received April 17, 2017;
ing by slow dropwise addition of propanꢀ2ꢀol (1.2 g, 0.02 mol)
in revised form May 22, 2017