2- and 3-Arylpropyl(ethynyl)dimethylsilanes

Article abstract of DOI:10.1007/s11176-005-0113-5

Hydrosilylation of ortho- and para-substituted 2-phenylpropenes and ortho-, meta-, and para-alkoxysubstituted 3-phenylpropenes with chlorodimethylsilane in the presence of H₂PtCl₆ was effected. The resulting adducts were reacted with ethyntlmagnesium bromide to synthesize 2- and 3-arylpropyl(ethynyl)silanes. 2004 MAIK "Nauka/Interperiodica".

Full text of DOI:10.1007/s11176-005-0113-5

Russian Journal of General Chemistry, Vol. 74, No. 12, 2004, pp. 1890 1894. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004,
pp. 2003 2006.
Original Russian Text Copyright
2004 by O. Yarosh, Zhilitskaya, N. Yarosh, Albanov, Voronkov.
2- and 3-Arylpropyl(ethynyl)dimethylsilanes
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 January 8, 2003
Abstract Hydrosilylation of ortho- and para-substituted 2-phenylpropenes and ortho-, meta-, and para-
alkoxysubstituted 3-phenylpropenes with chlorodimethylsilane in the presence of H2PtCl6 was effected. The
resulting adducts were reacted with ethyntlmagnesium bromide to synthesize 2- and 3-arylpropyl(ethynyl)-
silanes.
Earlier we studied hydrosilylation of 2-phenyl-
propene. Based on the structure of the resulting
adducts, by multistep procedure we synthesized
ethynyldimethyl(2-phenylpropyl)silane [1].
Developing these studies, we turned to hydro-
silylaltion of substituted propenes like
and B with chlorodimethylsilane in the presence of
A
H2PtCl6.
C=CH2 + HSiMe2Cl
CHCH2SiMe2Cl
X
X
Me
Me
A
I IV
X = 4-F (I), 4-Cl (II), 4-Me (III), 2-Et (IV).
CH2CH=CH2 + HSiMe2Cl
CH2CH2CH2SiMe2Cl
X
X
B
V XII
X = H (V), 2-MeO (VI), 3-MeO (VII), 4-MeO (VIII), 2-EtO (IX), 3-EtO (X), 4-EtO (XI), 4-i-PrO (XII).
The yields and constants of the reaction products
are listed in Table 1.
The reactions all are regioselective and involve
addition of the chlorodimethylsilyl group by the
Table 1. Constants of 2- and 3-aryl-substituted chlorodimethyl(propyl)silanes
Comp. no.
Yield, %
bp, C (p, mm Hg)
d240
n2D0
Formula
I
II
90
92
95
94
92
72
69
86
79
83
68
81
100 (1)
123 (2)
105 (1)
108 (1)
112 (2)
136 (2)
144 (2)
141 (1)
138 (1)
145 (1)
142 (1)
145 (1)
1.0741
1.1278
0.9626
1.0200
1.0400
1.0646
1.0446
1.0341
1.0323
1.0475
1.0518
1.0200
1.4865
1.5150
1.5000
1.5020
1.5015
1.5090
1.5055
1.5062
1.5015
1.5050
1.5045
1.5000
C11H16ClFSi
C11H16Cl2Si
C12H19ClSi
C13H21ClFSi
C11H17ClSi
C12H19ClOSi
C12H19ClOSi
C13H21ClOSi
C13H21ClOSi
C13H21ClOSi
C14H23ClOSi
III
IV
V
VI
VII
VIII
IX
X
XI
XII
1070-3632/04/7412-1890 2004 MAIK Nauka/Interperiodica

2- AND 3-ARYLPROPYL(ETHYNYL)DIMETHYLSILANES
1891
Table 2. Constants and elemental analyses of 2- and 3-aryl-substituted ethynyldimethyl(propyl)silanes
Found, %
H
Calculated, %
Si
Comp. Yield,
bp,
C
d240
n2D0
Formula
no.
%
(p, mm Hg)
C
Si
C
H
XIII
XIV
XV
66
64
65
68
66
66
64
64
66
63
66
64
102 (3)
107 (1)
102 (1)
105 (1)
95 (1)
0.9768 1.4855 70.45
0.9964 1.5125 65.28
0.9016 1.4992 77.38
0.9067 1.5022 77.78
0.9566 1.4935 77.10
8.09
7.24
9.38
9.70
8.94
8.70
8.82
8.71
8.84
8.78
8.75
9.72
12.81
11.35
12.85
12.46
13.43
11.98
11.99
12.03
11.31
11.45
11.43
10.01
C13H17FSi
C13H17ClSi
C14H20Si
C15H22Si
C13H18Si
C14H20OSi
C14H20OSi
C14H20OSi
C15H22OSi
C15H22OSi
C15H22OSi
C16H24OSi
70.85 7.77 12.72
65.93 7.24 11.86
77.70 9.32 12.98
78.18 9.63 12.19
77.16 8.96 13.88
72.35 8.68 12.09
72.35 8.68 12.09
72.35 8.68 12.09
73.12 8.99 11.40
73.12 8.99 11.40
73.12 8.99 11.40
73.78 9.28 10.78
XVI
XVII
XVIII
XIX
XX
XXI
XXII
XXIII
XXIV
76 (0.03) 0.9840 1.5055 72.23
78 (0.05) 0.9804 1.5055 71.98
90 (0.02) 0.9845 1.5060 72.41
89 (0.05) 0.9568 1.5010 73.00
92 (0.04) 0.9640 1.5020 73.25
88 (0.02) 0.9586 1.5010 72.75
82 (0.01) 0.9546 1.4965 73.78
terminal carbon atom of the propene irrespective of
the nature and position of the aromatic substituent in
the starting compound.
(CH2)3SiMe2Cl + BrMgC CH
CH2CH2CH2SiMe2C CH
X
We also found that organosilicon monomers I XII
react with ethynylmagnesium bromide to form cor-
responding ethynyl derivatives XIII XXIV.
X
XVII XXIV
X = H (XVII), 2-MeO (XVIII), 3-MeO (XIX), 4-MeO
(XX), 2-EtO (XXI), 3-EtO (XXII), 4-EtO (XXIII), 4-i-PrO
(XXIV).
CHCH2SiMe2Cl + BrMgC CH
X
Me
The yields, constants, and elemental analyses of
compounds XIII XXIV are listed in Table 2. Struc-
tural assessment of the products was performed by
CHCH2SiMe2C CH
X
Me
XIII XVI
1
means of H, 13C, and 29Si spectroscopy (Tables 3
and 4). They are colorless liquids readily distillable
in a vacuum.
X = 4-F (XIII), 4-Cl (XIV), 4-Me (XV), 2-Et (XVI).
Table 3. 1H, 13C, and 29Si NMR spectra of compounds XIII XVI
Y SiMe2C CH [Y = CH(CH3)CH2]
X
1H NMR spectrum, , ppm
=CH
X (Comp. no.)
SiMe
Y
Ho (X)
Ho (CH)
4-Fa
(XIII)
0.06,
0.12
1.10 (7.5) (CH2Si),
1.37 (6.8) (MeCH),
3.04 (6.8) (MeCH)
1.01 (7.5) (CH2Si),
1.28 (6.8) (MeCH),
2.97 (7.1) (MeCH)
2.38
2.32
6.99
(8.6)
7.22
(8.6)
4-Cl
(XIV)
0.05,
0.01
7.20
(8.5)
7.12
(8.5)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1892
YAROSH et al.
Table 3. (Contd.)
1H NMR spectrum, , ppm
X (Comp. no.)
SiMe
Y
=CH
2.33
Ho (X)
Ho (CH)
4-Meb
(XV)
0.03,
0.01
1.03 (14.7);
7.05
(8.2)
7.05
(8.2)
1.06 (7.6) (CH2Si),
1.30 (7.1) (MeCH),
2.96 (7.1) (MeCH)
1.03 (14.38);
1.06 (6.8) (CH2Si),
1.29 (7.06) (MeCH),
3.31 (7.06) (MeCH)
2-Etc
(XVI)
0.00,
0.09
2.28
13C NMR spectrum, C, ppm
29Si NMR spectrum,
Si, ppm
X (Comp. no.)
SiMe
Y
CH
Ci
Co
Cm
Cp
4-Fa
(XIII)
0.95,
1.53
26.38 (CH2Si),
26.27 (MeCH),
35.64 (MeCH)
26.07 (CH2Si),
25.96 (MeCH),
35.84 (MeCH)
27.00 (CH2Si),
26.19 (MeCH),
35.84 (MeCH)
26.32 (CH2Si),
25.98 (MeCH),
30.14 (MeCH)
94.23
(89.07)
161.28 114.98 127.97 144.57
(240) (21) (8) (3)
16.38
16.23
16.90
16.14
4-Cl
(XIV)
0.93,
1.48
94.23
(89.01)
131.53 128.45 128.05 147.47
135.21 129.03 126.59 146.09
4-Meb
(XV)
0.89,
1.54
93.84
(89.51)
2-Etc
(XVI)
0.57,
1.14
(89.52)
a 3
4
b
c
J
8.6,
J
5.4 Hz.
(CH -p) 2.30, (CH -p) 21.07 ppm.
(Et ): 1.50 (CH ), 2.95, 3.04 (CH ), 6.68, 6.95 (Ar);
o 3 2
FCCH
FCCCH
3
C
3
3,4,5,6
(Et ): 16.12 (CH ), 147.09 (C CH), 140.50 (C Et), 128.82, 126.42, 126.00, 125.87 ppm (C
).
C
o
3
i
i
Table 4. 1H, 13C, and 29Si NMR spectra of compounds XIII XV
Y SiMe2C CH [Y = (CH2)3]
X
X
1H NMR spectrum, , ppm
CH
(Comp. no.)
SiMe
0.15
Y
Ar
X
H
(XVII)
0.66 (CH2Si),
1.71 (CH2),
2.65 (CH2Ph)
0.84 (CH2Si),
1.88 (CH2),
2.84 (CH2Ph)
0.90 (CH2Si),
1.95 (CH2),
2.31
2.37
2.58
7.14 (Ho,p),
7.24 (Hm)
2-MeO
(XVIII)
0.31
0.40
6.86,
6.97,
7.22
3.84
3.97
3-MeO
(XIX)
6.96 (H2),
6.94 (H4),
6.99 (H6),
7.39 (H5)
2.86 (CH2Ph)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

2- AND 3-ARYLPROPYL(ETHYNYL)DIMETHYLSILANES
1H NMR spectrum, , ppm
1893
Table 4. (Contd.)
X
(Comp. no.)
SiMe
0.33
Y
CH
Ar
X
4-MeO
(XX)
0.82 (CH2Si),
1.86 (CH2),
2.51
6.97,
7.23
3.88
2.75 (CH2Ph)
0.83 (CH2Si),
1.84 (CH2),
2-EtO
(XXI)
0.30
2.44
6.90,
6.97,
7.24
1.51
(Me),
4.09
2.80 (CH2Ph)
(OCH2)
1.48
(Me),
4.08
1.47
(Me),
4.07
1.40
(Me),
4.56
3-EtO
(XXII)
0.26
0.28
0.26
0.76 (CH2Si),
1.82 (CH2),
2.72 (CH2Ph)
0.76 (CH2Si),
1.80 (CH2),
2.69 (CH2Ph)
0.76 (CH2Si),
1.79 (CH2),
2.44
2.45
2.44
6.86 6.78,
(H2,4,6),
7.25 (H5)
6.89,
4-EtO
(XXIII)
7.17
4-i-PrO
(XXIV)
6.89,
7.16
2.68 (CH2Ph)
(OCH2)
13C NMR spectrum, C, ppm
X
29Si NMR spectrum,
(Comp. no.)
ppm
Si,
SiMe
Y
X
Ar
C
HC
H
(XVII)
1.83
15.58 (CH2Si),
25.68 (CH2),
39.35 (CH2Ph)
125.76 (Cp),
128.21 (Co,m),
128.45 (Co,m),
142.25 (Ci)
110.08, 120.48, 88.79 93.74
126.95, 130.03,
130.71 (Ci),
157.60 (Ci)
110.80, 120.82, 89.01 93.80
114.25, 129.07,
85.27 93.76
15.2
15.3
15.2
16.1
2-MeO
(XVIII)
1.90
2.02
2.12
15.98 (CH2Si),
24.23 (CH2),
33.92 (CH2Ph)
54.68
(OMe)
3-MeO
(XIX)
15.50 (CH2Si),
25.49 (CH2),
38.28 (CH2Ph)
54.84
(OMe)
143.80 (Ci),
159.52 (Ci)
4-MeO
(XX)
15.32 (CH2Si),
25.72 (CH2),
38.23 (CH2Ph)
54.84
(OMe)
113.49 (C3,5),
129.12 (C2,6),
134.14 (C1),
157.54 (C4)
88.95 93.68
2-EtO
(XXI)
2.01
1.91
15.85 (CH2Si),
23.94 (CH2),
33.84 (CH2Ph)
14.88
(CH3),
63.17
111.10, 120.11, 89.23 93.54
126.77, 129.87,
15.2
15.2
130.80 (C1),
156.75 (C2)
3-EtO
(XXII)
15.63 (CH2Si),
25.61 (CH2),
39.42 (CH2Ph)
14.90
(CH3),
63.13
114.16 (C3,5),
129.12 (C2,6),
134.91 (C1),
156.95 (C4)
89.12 93.85
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1894
YAROSH et al.
Table 4. (Contd.)
13C NMR spectrum, C, ppm
X
29Si NMR spectrum,
(Comp. no.)
ppm
Si,
SiMe
2.06
Y
X
Ar
C
HC
4-EtO
(XXIII)
15.39 (CH2Si),
25.77 (CH2),
38.32 (CH2Ph)
14.76
(CH3),
63.09
115.68 (C3,5),
129.22 (C2,6),
134.15 (C1),
155.89 (C4)
114.16 (C3,5),
129.12 (C2,6),
134.91 (C1),
156.95 (C4)
88.98 93.70
15.2
15.2
4-i-PrO
(XXIV)
2.02
15.46 (CH2Si),
25.79 (CH2),
38.40 (CH2Ph)
22.02
(CH3),
69.63
89.02 93.71
Compounds XVIII XXIV have a pleasant odor.
Ethynyl[2-(4-fluorophenyl)propyl]dimethyl-
silane (XIII). Ethynylmagnesium bromide prepared
from 1.21 g of Mg, 5.45 g of EtBr, and acetylene in
100 ml of THF was added dropwise with stirring to
11.5 g of compound I in 50 ml of ether. The reaction
mixture was stirred for 1 h and then decomposed with
water and 5% HCl. After usual workup and drying
over calcined CaCl2, the solvents were distilled off at
reduced pressure (water-jet pump), and the residue
was distilled in a vacuum to isolate 7.2 g (66.2%) of
compound XIII (Table 2).
The starting 2-arylpropenes were prepared by a
usual reaction of the corresponding phenylmagnesium
bromides with acetone followed by dehydration of the
resulting tertiary alcohols over p-toluenesulfonic acid.
3-Arylpropenes were synthesized by the reaction of
alkoxyphenylmagnesium bromides with 3-bromo-
propene. Allylbenzene is a commercial product.
EXPERIMENTAL
The NMR spectra were obtained on a Bruker DRX-
400 spectrometer (400 MHz) for 15% solutions in
CDCl3, internal reference HMDS.
Compounds XIV XXIV were prepared in a similar
way (Table 2).
ACKNOWLEDGMENTS
Chloro[2-(4-fluorophenyl)propyl]dimethylsilane
(I). Chlorodimethylsilane, 5.7 g, was added dropwise
with stirring to a mixture of 8.2 g of 2-(4-fluoro-
phenyl)propene and 0.1 ml of 0.2 N H2PtCl6 in
2-propanol. The mixture was heated for 0.5 h at 90 C
and distilled in a vacuum. Yield 12.5 g (90.5%)
(Table 1).
The work was financially supported by the Russian
Foundation for Basic Resesarch (project no. 00-15-
97395).
REFERENCES
1. Yarosh, O.G., Burnashova, T.D., Yarosh, N.K., and
Voronkov, M.G., Zh. Obshch. Khim., 2000, vol. 70,
no. 10, p. 1652.
Compounds II XII were prepared in a similar way
(Table 1).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004