Cyclosilethynes containing exocyclic cyclopentyl and cyclohexyl groups

Article abstract of DOI:10.1007/s11176-005-0135-z

The reaction of BrMgC≡CSiMe₂C≡CSiMe ₂C≡CSiMe₂C≡CSiMe₂C≡CMgBr with chloro(cyclopentyl)(methyl)silane in a large excess of THF gave 1-cyclopentyl-1,4,4,7,7,10,10,13,13-nonamethyl-1,4,7,10, 13- pentasilacyclopentadeca-2,5,8,11,14-pentayne. Similarly, 1,10-di(cyclopentyl)- or 1,6-di(cyclopentylmethyl)-1,4,4,7,7,10,13,13,16,16-decamethyl-1,4,7,10,13,16- hexasilacyclooctadeca-2,5,8,11,14,17-hexaynes were synthesized from BrMgC≡₂C≡CSiMe₂C≡CMgBr and dichloro(cyclopentyl)methylsilane or dichloro(cyclopentylmethyl)(methyl)silane. Condensation of Me₂Si(C≡CMgBr)₂ with dichloro(cyclohexyl)-methylsilane afforded 1,7-di(cyclohexyl)-1,4,4,7,10,10- hexamethyl-1,4,7,10-tetrasilacyclododeca-2,5,8,11-tetrayne. 2004 MAIK "Nauka/Interperiodica".

Full text of DOI:10.1007/s11176-005-0135-z

Russian Journal of General Chemistry, Vol. 74, No. 8, 2004, pp. 1185 1187. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004,
pp. 1282 1284.
Original Russian Text Copyright
2004 by O. Yarosh, Zhilitskaya, N. Yarosh, Albanov, Klyba, Voronkov.
Cyclosilethynes Containing Exocyclic Cyclopentyl
and Cyclohexyl Groups
O. G. Yarosh, L. V. Zhilitskaya, N. K. Yarosh,
A. I. Albanov, L. V. Klyba, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
Received August 26, 2002
Abstract The reaction of BrMgC CSiMe2C CSiMe2C CSiMe2C CSiMe2C CMgBr with chloro(cyclo-
pentyl)(methyl)silane in a large excess of THF gave 1-cyclopentyl-1,4,4,7,7,10,10,13,13-nonamethyl-1,4,7,10,
13-pentasilacyclopentadeca-2,5,8,11,14-pentayne. Similarly, 1,10-di(cyclopentyl)- or 1,6-di(cyclopentyl-
methyl)-1,4,4,7,7,10,13,13,16,16-decamethyl-1,4,7,10,13,16-hexasilacyclooctadeca-2,5,8,11,14,17-hexaynes
were synthesized from BrMgC CSiMe2C CSiMe2C CMgBr and dichloro(cyclopentyl)methylsilane or di-
chloro(cyclopentylmethyl)(methyl)silane. Condensation of Me2Si(C CMgBr)2 with dichloro(cyclohexyl)-
methylsilane afforded 1,7-di(cyclohexyl)-1,4,4,7,10,10-hexamethyl-1,4,7,10-tetrasilacyclododeca-2,5,8,11-
tetrayne.
Proceeding with the research into perorganylcyclo-
silethynes [R2SiC C]n [1, 2] and coming nearer to the
synthesis of macrocyclic propellanes, we have
prepared new representatives of this class of com-
pounds, containing cyclic peripheral groups. Thus,
the reaction of bis[[(bromomagnesioethynyl)dimethyl-
silylethynyl]dimethylsilyl]ethyne with dichloro(cyclo-
pentyl)methylsilane in THF under conditions of high
dilution gave 1-cyclopentyl-1,4,4,7,7,10,10,13,13-
nonamethyl-1,4,7,10,13-pentasilacyclopentadeca-2,5,
8,11,14-pentayne (I).
Me Me
1
Si
C
C
Me2SiC CSiMe2C CMgBr
2 Me
C
C
Me
Me
Me
C
Si
Si
+ Cl2Si
C
C
C
Me2SiC CSiMe2C CMgBr
C
C
Si
C C
Si
Me
Me
Me
Me
I
Similarly, 1,10-dicyclopentyl)- or 1,6-di(cyclo-
pentylmethyl)-1,4,4,7,7,10,13,13,16,16-decamethyl-
1,4,7,10,13,16-hexasilacyclooctadeca-2,5,8,11,14,17-
hexaynes (compounds II and III, respectively) were
synthesized from bis[(bromomagnesioethynyl)di-
methylsilyl)ethyne and dichloro(cyclopentyl)methyl-
silane or dichloro(cyclopentylmethyl)(methyl)silane.
Finally, the reaction of bis(bromomagnesioethynyl)-
dimethylsilane with dichloro(cyclohexyl)(methyl)-
silane under the same conditions resulted in prepara-
tion of 1,7-di(cyclohexyl)-1,4,4,7,10,10-hexamethyl-
1,4,7,10-tetrasilacyclododeca-2,5,8,11-tetrayne (IV).
Compounds I IV are colorless high-melting crys-
1070-3632/04/7408-1185 2004 MAIK Nauka/Interperiodica

1186
YAROSH et al.
Table 1. Properties of compounds I IV
Found, %
Calculated, %
H
Comp.
no.
Yield,
%
[M], m/e
(Irel, %)
mp, C
Formula
C
H
Si
C
Si
30.20
28.02
26.78
24.19
I
II
III
IV
10.2
8.8
8.5
4.4
167
186
173
193
474 (20)
600 (16)
628 (16)
464 (20)
62.12
63.57
64.25
67.14
8.02
8.24
8.43
8.88
29.91
27.67
26.74
23.53
C24H36Si5
C32H48Si6
C34H52Si6
C26H40Si4
61.99
63.93
64.89
67.32
7.08
8.05
8.33
8.67
Table 2. 1H, 13C, and 29Si NMR spectra of compounds I IV
29Si NMR spectrum,
Si, ppm
1H NMR spectrum, , ppm
13C NMR spectrum, C, ppm
Comp.
no.
2
1
Si1CH3
0.33
Si2CH3
0.29
Si C5H9
1.56
Si1CH3 Si2CH3
C C
Si1
Si2
3
I
0.11
0.00
0.02
2.56
2.73
1.00
110.07,
110.85,
111.11
109.90,
110.68,
110.94
110.71,
110.92,
111.16
25.01 (C1),
27.22 (C2),
27.93 (C3)
24.84 (C1),
26.99 (C2),
27.70 (C3)
22.54 (CH2Si),
24.93 (C2),
35.33 (C3),
35.56 (C1)
41.6
41.4
41.58
36.8
II
III
0.33
0.28
1.58
36.7
0.33
0.28
1.00
(CH2Si),
1.57
41.55
IVa
0.34
0.33
0.95
4.88
112.55,
114.55
41.92
36.86
a
1
13
1
4
Other signals: H NMR spectrum, , ppm: 1.81 (
); C NMR spectrum,
, ppm: 22.35 (C ), 26.33 (C ), 26.51
C
2
3
3
2
1
(C ), 27.33 (C ) (
).
4
tals insoluble in nonpolar solvents. Their melting
points, yields, and elemental analyses are listed in
Table 1. The structure of the products was proved by
1H, 13C, and 29Si NMR spectroscopy (Table 2) and
mass spectrometry (Table 1).
Dichloro(cyclohexyl)(methyl)silane was prepared
by the addition of dichloro(methyl)silane to cyclo-
Me
Me
Me
Me
1
Si C C Si
C
Me2SiC CMgBr
C
C
Me
R
C
C
C
Me
Me
2
Si
Si
+ 2Cl2SiMeR
2
C
C
C
C
Me2SiC CMgBr
Si
C C
Si
Me
Me
Me
Me
II, III
R =
(II),
(III).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004

CYCLOSILETHYNES CONTAINING EXOCYCLIC CYCLOPENTYL
1187
Me
Me Si1C C Si2
Me
Me
C
C
C
C
2Me2Si(C CMgBr)2 + 2Cl2Si
Si C C Si Me
IV
hexene in the presence of H2PtCl6 under autopressure
calcined CaCl2, removal of the solvents, and high-
vacuum distillation (10 mm Hg) gave 0.95 g (10%)
of compound I (Table 1). Compounds II IV were
prepared in a similar way (Table 1).
at 180 C, yield 45%, bp 68 C (2 mm Hg), d420
4
1.1344, n2D0 1.4695. The other starting materials were
described earlier [3 5].
REFERENCES
EXPERIMENTAL
1. Yarosh, O.G., Voronkov, M.G., and Brodskaya, E.I.,
The mass spectra were obtained on an LKB-2091
GC MS system with direct inlet (ion source tempera-
ture 250 C), ionizing energy 60 eV. The NMR spectra
were obtained on a Jeol FX-90Q spectrometer (15%
solutions in CDCl3, internal reference TMS).
Usp. Khim., 1995, vol. 64, no. 9, p. 896.
2. Voronkov, M.G., Zhilitskaya, L.V., Yarosh, O.G., Al-
banov, A.I., and Klyba, L.V., Zh. Obshch. Khim., 1997,
vol. 67, no. 12, p. 2006.
1-Cyclopentyl-1,4,4,7,7,10,10,13,13-nonamethyl-
1,4,7,10,13-pentasilacyclopentadeca-2,5,8,11,14-
pentayne (I). To 50 ml of ether we added with stir-
ring simultaneously from two dropping funnels the
Iotsich reagent prepared from 0.96 g of Mg and 4.36 g
of EtBr, HC CSiMe2C CSiMe2C CSiMe2C
CSiMe2C CH, 7.8 g, in 50 ml of THF, and 3.68 g of
dichloro(cyclopentyl)methylsilane in 50 ml of ether.
The mixture was stirred for 1 h and decomposed with
water and 5% HCl. Conventional workup, drying over
3. Yarosh, O.G., Ivanova, Z.G., Burnashova, T.D., and
Voronkov, M.G., Izv. Ross. Akad. Nauk, Ser. Khim.,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 8 2004