Hydrosilylation of cyclohexene, 1-methylcyclohexene, and isopropylidenecyclohexane

Article abstract of DOI:10.1007/s11176-005-0114-4

Hydrosilylation of cyclohexene and isopropylidenecyclohexane with chloro(methyl)silanes Me_3-n SiHCl_n (n = 1-3) gives rise to cyclohexyl- and chloro(2-cyclohexylpropyl)methylsilanes. Hydrosilylation of 1-methylcyclohexene with chlorodimethylsilane (n = 1) occurs anomalously and involves double-bond migration to form a mixture of seven compounds: the cis and trans isomers of 2-, 3-, 4-chlorodimethyl(methylcyclohexyl)silanes and chlorodimethyl(cyclohexylmethyl)silane. Chlorodimethylsilane (n = 2) adds to 1-methylcyclohexene to form a mixture of the cis and trans isomers of dichloro(methyl)(2-methylcyclohexyl)silane and dichloro(cyclohexylmethyl) methylsilane. With trichlorosilane (n = 3), no other products than trichloro(cyclohexylmethyl)silane are formed. The hydrosilylation products were reacted with ethynylmagnesium bromide to synthesize the corresponding ethynyl derivatives. 2004 MAIK "Nauka/Interperiodica".

Full text of DOI:10.1007/s11176-005-0114-4

Russian Journal of General Chemistry, Vol. 74, No. 12, 2004, pp. 1895 1899. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004,
pp. 2007 2011.
Original Russian Text Copyright
2004 by O. Yarosh, Zhilitskaya, N. Yarosh, Albanov, Voronkov.
Hydrosilylation of Cyclohexene, 1-Methylcyclohexene,
and Isopropylidenecyclohexane
O. G. Yarosh, L. V. Zhilitskaya, N. K. Yarosh, A. I. Albanov, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
Received February 12, 2003
Abstract Hydrosilylation of cyclohexene and isopropylidenecyclohexane with chloro(methyl)silanes
Me3 nSiHCln (n = 1 3) gives rise to cyclohexyl- and chloro(2-cyclohexylpropyl)methylsilanes. Hydrosilyla-
tion of 1-methylcyclohexene with chlorodimethylsilane (n = 1) occurs anomalously and involves double-bond
migration to form a mixture of seven compounds: the cis and trans isomers of 2-, 3-, 4-chlorodimethyl(methyl-
cyclohexyl)silanes and chlorodimethyl(cyclohexylmethyl)silane. Chlorodimethylsilane (n = 2) adds to 1-
methylcyclohexene to form a mixture of the cis and trans isomers of dichloro(methyl)(2-methylcyclohexyl)-
silane and dichloro(cyclohexylmethyl)methylsilane. With trichlorosilane (n = 3), no other products than tri-
chloro(cyclohexylmethyl)silane are formed. The hydrosilylation products were reacted with ethynylmagnesium
bromide to synthesize the corresponding ethynyl derivatives.
Hydrosilylation of cycloalkenes and alkylidene-
cycloalkenes has poorly been studied [1 5]. It is
known that cyclopentene and 1-methylcyclopentene
react with hydrosilanes to form respectively chloro-
(cyclopentyl)methyl- and chloro(cyclopentylmethyl)-
methylsilanes, which were then converted into ethynyl
derivatives [6, 7].
chloro(methyl)-, and trichlorosilanes of the general
formula Me3 nSiHCln (n = 1 3) in the presence of
H2PtCl6. The reaction occurs at 180 C. The yields of
hydrosilylation products are 15 30, 40 50, and 45
60%, respectively. The reactions of cyclohexene with
Me3 nSiHCln at all n afford chloro(cyclohexyl)-
methylsilanes.
Petrov et al. [8] showed that dichloro(methyl)silane
adds to cyclohexene in the presence of platinum on
carbon (0.5%) at 220 C to form dichloro(cyclohexyl)-
methylsilane in a low (6%) yield [8]. The nickel
complex catalyst Ni(PPhMe2)Cl2 is more active: Di-
chloro(methyl)silane adds to cyclohexene (120 C,
20 h) to give a mixture of dichloro(cyclohexyl)me-
thylsilane (34%) and chloro(cyclohexyl)methylsilane
(41%) [9]. The addition of dichloro(methyl)silane to
1-methylcyclohexene in the presence of H2PtCl6 gives
rise to chloro(cyclohexylmethyl)methylsilane [10].
The reactions of trichlorosilane with 1- or 3-methyl-
cyclohexene provide trichloro(cyclohexylmethyl)-
silane [11].
+ Me3 nSiHCln
SiMe3 nCln,
I III
n = 1 (I), 2 (II), 3 (III).
1-Methylcyclohexene is hydrosilylated regio- and
stereoselectively. The structures of the adducts are
determined by the number of chlorine atoms (n) in
the hydrosilylating agent. Thus chlorodimethylsilane
forms a mixture of seven hydrosilylation products:
chloro(cyclohexylmethyl)dimethylsilane (IV), cis- and
trans-chloro(2-methylcyclohexyl)dimethylsilane (V),
cis- and trans-chloro(3-methylcyclohexyl)dimethyl-
silane (VI), and cis- and trans-chloro(4-methylcyclo-
hexyl)dimethylsilane (VII).
We performed a systematic study of hydrosilyla-
tion of cyclohexene, 1-methylcyclohexene, and iso-
propylidenecyclohexane with chlorodimethyl-, di-
__
.
.
.
.
.
SiMe2Cl
.
.
__
.
|
..
....
.SiMe2Cl
__
.
|
..
....
.SiMe2Cl +
Me + Me2SiHCl
+
_
IV
cis-V
trans-V
.
.
.
.
.
.
.
.
__
.
.
|
..
....
.SiMe2Cl
__
.
__
..
.
|
.
..
....
+
__
| ..
.SiMe2Cl
.
|
..
....
.SiMe Cl
+
__
+
.
|
..
....
.SiMe2Cl
2
+
cis-VI
trans-VI
cis-VII
trans-VII
1070-3632/04/7412-1895 2004 MAIK Nauka/Interperiodica

1896
YAROSH et al.
The reaction of dichloro(methyl)silane with
1-methylcyclohexene gave dichloro(cyclohexylme-
thyl)methylsilane (VIII) and cis- and trans- dichloro-
(2-methylcyclohexyl)methylsilanes (IX).
__
.
.
.
.
SiMeCl2
.
.
.
__
__
.
|
..
....
.
|
..
....
.SiMeCl2
.SiMeCl2
+
Me + MeSiHCl2
+
VIII
cis-IX
trans-IX
Trichlorosilane reacts with 1-methylcyclohexene
to form exclusively trichloro(cyclohexylmethyl)silane
(X), yield 60%.
+ Me3 nSiHCln
SiCl3
SiMe3 nCln
Me + HSiCl3
XI XIII
X
The reaction of isopropylidenecyclohexane with
all the hydrosilylating agents gives chloro(2-cyclo-
hexylpropyl)methylsilanes XI XIII.
Compounds I XIII were reacted with ethynyl-
magnesium bromide in THF to synthesize ethynyl
derivatives XIV XXVI.
R SiMe3 nCln + nBrMgC CH
R SiMe3 n(C CH)n,
XIV XXVI
, n = 1 (XVII), 2 (XXI), 3 (XXIII);
, n = 1 (XIV), 2 (XV), 3 (XVI); R =
R =
R =
__
.
.
.
.
.
.
.
__
.
|
..
....
.
, n = 1 (trans-XVIII), 2 (trans-XXII);
__
.
|
..
....
.
, n = 1 (cis-XVIII), 2 (cis-XXII); R =
_
.
.
.
.
.
.
.
.
.
__
__
__
, n = 1 (cis-XX);
.
|
.
|
..
.
..
....
....
..
__
.
| ..
.
.
|
, n = 1 (trans-XIX), R =
..
....
.
, n = 1 (cis-XIX), R =
R =
.
__
.
|
..
....
.
, n = 1 (XXIV), 2 (XXV), 3 (XXVI).
, n = 1 (trans-XX),; R =
R =
(Cyclohexylmethyl)triethynylsilane (XXIII) is a
colorless substance (mp 66 C), and the other ethynyl
derivatives XIV XXII and XIV XXVI are colorless
liquids distillable in a vacuum and stable to handling.
The yields and constants of hydrosilylation products
I XIII and their ethynyl derivatives XIV XXVI are
listed in Tables 1 and 2, respectively. The structures
EXPERIMENTAL
The NMR spectra were recorded on a Bruker DPX-
400 spectrometer (400 MHz) for 15% solutions in
CDCl3, internal reference HMDS.
Trichloro(cyclohexylmethyl)silane (X). A mixture
of 9.6 g of 1-methylcyclohexene, 13.55 g of trichloro-
silane, and 0.02 ml of H2PtCl6 in 2-propanol was
1
of compounds XIV XXVI are established by H, 13C,
and 29Si spectroscopy (Table 3).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

HYDROSILYLATION OF CYCLOHEXENE, 1-METHYLCYCLOHEXENE
1897
Table 1. Yields and constants of chlorosilanes I XIII
heated (5 h at 120 C and 5 h at 180 C) in an ampule
housed in an autoclave and then distilled in a vacuum.
Yield 13.8 g (60%) (Table 1).
Comp.
no.
Yield,
%
bp,
C
d240
n2D0
(p, mm Hg)
Compounds I IX and XI XIII were prepared in a
similar way (Table 1).
I
II
III
IV VII
VIII, IX
X
XI
XII
17
46
51
21
51
60
32
41
46
74 (10)
68 (2)
67 (1)
80 (4)
83 (3)
85 (4)
99 (1)
110 (3)
115 (4)
0.9853
1.1344
1.2469
0.9721
1.0759
1.1765
0.9528
1.0569
1.1896
1.4525
1.4695
1.4755
1.4508
1.4735
1.4755
1.4640
1.4740
1.4775
(Cyclohexylmethyl)triethynylsilane (XXIII). To
11.6 g of compound X in 50 ml of ether we added
dropwise with stirring ethynylmagnesium bromide
prepared from 3.65 g of Mg, 16.5 g of EtBr, and
cetylene in 120 ml of THF. After 30-min stirring, the
mixture was decomposed with water and 5% HCl,
subjected to usual workup, dried with CaCl2, the sol-
vents were removed at reduced pressure (water-jet
vacuum), and the residue was sublimed in a vacuum
XIII
Table 2. Yields, constants, and elemental analyses of ethynylsilanes XIV XXVI
Found, %
Calculated, %
H Si
Comp.
no.
Yield,
%
bp,
C
d240
n2D0
Formula
(p, mm Hg)
C
H
Si
C
XIV
XV
XVI
XVII XX
XXI, XXII
XXIII
XXIV
XXV
67
65
64
71
66
63
67
69
65
83 (10)
80 (4)
85 (1)
70 (10)
55 (1)
66a
95 (1)
103 (1)
110 (1)
0.8762 1.4550
0.9187 1.4760
0.9310 1.4895
0.8846 1.4465
0.9034 1.4730
71.73 10.68 17.20
C10H18Si
C11H16Si
C12H14Si
72.20 10.90 16.89
74.15
77.17
9.33 16.01
7.78 15.29
74.92
77.34
73.25
75.71
77.92
9.15 15.33
7.57 15.08
11.18 15.57
9.53 14.75
8.05 14.02
72.80 10.92 16.02 C11H20Si
75.78
9.54 14.59
C12H18Si
C13H16Si
C13H24Si
C14H22Si
C15H20Si
78.16
8.00 13.99
0.8664 1.4645
0.8958 1.4765
0.9245 1.4860
74.97 11.72 13.79
75.68 10.15 12.71
74.91 11.61 13.48
76.98 10.15 12.86
XXVI
77.78
9.14 11.73
78.88
8.82 12.30
a
Melting point.
Table 3. 1H, 13C, and 29Si NMR parameters of compounds XIV XXVI
4
Y SiMe3 n(C CH)n [Y = O, CH2, CH(CH3)CH2]
1
3
2
Comp.
no.
1H NMR spectrum, , ppm
R
13C NMR spectrum, C, ppm
CH SiC
29Si NMR
spectrum,
Si, ppm
SiMe
CH
SiMe
R
XIV
XV
0.07 s 0.63 m, 1.16 m, 1.69 m
0.28 s 0.80 m, 1.23 m, 1.76 m
0.92 m, 1.28 m, 1.80 m
2.29
2.41
2.54
3.95 25.38 (C1), 26.76 (C4), 93.64 88.56
27.02 (C3), 27.81 (C2)
13.40
34.21
60.09
3.65 26.19 (C1), 26.31 (C4), 95.19 84.96
26.79 (C3), 27.76 (C2)
XVI
25.27 (C1), 26.22 (C4), 96.24 81.63
27 52
26.69 (C3),
.
(C2)
XVII 0.07 s, 0.61 d (SiCH2), 0.86 d.d.d 2.29,
0.88 22.68 (SiCH2), 26.21 92.03, 89.75, 19.50, 19.24,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1898
YAROSH et al.
Table 3. (Contd.)
Comp.
no.
1H NMR spectrum, , ppm
13C NMR spectrum, C, ppm
CH SiC
29Si NMR
spectrum,
Si, ppm
SiMe
R
CH
SiMe
R
XX
0.10 s, (4Ha), 0.96 q.t (4Ha), 1.04 d.t 2.30,
0.12 s, (3Ha), 1.18 d.t (4He), 1.28 m 2.34,
(C4), 26.48 (C3), 35.48 93.26, 89.85 19.01, 17.47,
(C1), 36.58 (C2), 35.89 93.48,
(C1), 37.74 (C2)
93.69
16.75, 16.48
0.16 s (3He)
2.35
XXI
0.35 s 0.75 d (SiCH2), 0.98 d.d.d
(2.6Ha)
2.41
0.66 23.14 (SiCH2), 26.25 94.89 86.11
38.25
XXII
1.18 q.t (4Ha), 1.25 q.t
2.42,
2.43
(C4), 26.49 (C4), 26.68 95.07,
(C3), 26.84 (C3), 33.86 96.24
(C1), 34.15 (C1), 35.15
34.29,
33.89
(3.5Ha), 1.60
1.66 d.t (3.5He), 1.70 m (1Ha),
1.82 (2.6He)
m
(4He),
m
(C1), 35.34 (C2), 35.48
(C2), 36.40 (C2)
XXIII
0.90 d (SiCH2), 1.04 d.d.d
(2.6Ha), 1.65 q.t (4Ha),
1.27 q.t (3Ha), 1.63 m (4He),
1.67 m (1He), 1.71 m (3He),
2.55
2.34
23.93 (SiCH2), 25.96 95.60 82.68
63.97
15.74
(C4), 26.19 (C3), 33.67
(C1),
35.96
(C2)
1.86
d.q
(2He)
XXIV 0.17 s 0.49 d.d [A part of the AB
0.85 19.21 (CH3), 21.15
(SiCH2), 26.92 (C4),
27.05 (C3), 34.61 (C1)
[30.36 (C2), 28.81 (C2)]
(nonequiv.), 45.39
(CHCH3)
93.60 89.99
system of SiCH2, 2JAB 14.69,
3J(HACCH) 9.72 Hz], 0.76 d.d
[B part of the AB system of
SiCH2,2JAB 14.69, 3J(HBCCH)
4.3 Hz], 0.90 d (CH3, J
6.8 Hz), 0.99 m (2Ha), 1.18 m
(3Ha, CH, 1Ha), 1.62 m (4Ha,
4He, 3He), 1.72 d.t (2He)
XXV 0.34 s 0.63, 0.90 [SiCH2, AB spec-
2.45
2.55
0.86 18.92 (CH3), 20.69
(SiCH2), 26.74 (C4),
26.89 (C3), 34.38 (C1)
[30.25 (C2), 28.62 (C2)]
94.84 86.06
95.87 82.79
37.10
62.86
2
3
trum, JAB 14.55, J(HACCH)
9.78, 3J(HBCCH) 4.5 Hz],
0.95 d (CH3CH), 0.99 m
(2Ha), 1.3 0.98 (1Ha, 3Ha,
2Ha, CH), 1.79 1.56 (4Ha,
4He, 3He, 2He)
(nonequiv.)
44.99
(CHCH3)
XXVI
0.77, 0.88 (SiCH2), 0.99 d
(CH3CH), 1.3 0.98 (1Ha,
3Ha, 2Ha, CH), 1.79 1.56
(4Ha, 4He, 3He, 2He)
18.74 (CH3), 20.80
(SiCH2), 26.63 (C4),
26.83 (C3), 34.14 (C1)
[30.21 (C2), 28.54 (C2)]
(nonequiv.), 44.74
(CHCH3)
(1 mm Hg) on a boiling water bath to isolate 6.6 g
(63%) of compound XXIII (Table 2).
REFERENCES
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vanie, gidrogermilirovanie gidrostannilirovanie
Compounds XIV XXII and XXIV XXVI were
prepared in a similar way (Table 2).
i
(Hydrosilylation, Hydrogermylation, and Hydrostan-
nylation), Riga: Zinatne, 1964.
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project no. 00-15-
97395).
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HYDROSILYLATION OF CYCLOHEXENE, 1-METHYLCYCLOHEXENE
1899
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