CHEMISTRY

Academician A. V. TOPCHIEV, N. S. NAMETKIN, and F. F. MACHUS

SOME SILICON HYDROCARBONS OF THE DISILANEMETHANE AND DISILANEETHANE SERIES

In a number of previous communications we described silicon hydrocarbons of the disilanemethane and disilaneethane series, obtained by the interaction of organomagnesium compounds with hexachloro-, pentachloro-, and tetrachloro derivatives of disilanemethane and with hexachlorodisilaneethane \((^{1-6})\). The possibility was also shown of the addition reaction of pentachloro- and tetrachlorodisilane to unsaturated hydrocarbons, leading to the formation of alkyl- and dialkylchloro derivatives of disilanemethane \((^7)\).

In the present communication, silicon hydrocarbons of the disilanemethane series with various organic radicals are described, obtained by the interaction of organolithium compounds with alkyl- and dialkylchloro derivatives of disilanemethane described by us earlier \((^7)\), as well as hexaalkyl derivatives of disilanemethane and disilaneethane, obtained by the interaction of organomagnesium compounds with hexachlorodisilanemethane and hexachlorodisilaneethane.

Table 1 gives the properties of the silicon hydrocarbons obtained.

Experimental Part

1. Preparation of hexyltetraethyldisilanemethane.
To ethylmagnesium bromide, prepared from 33 g of ethyl bromide, 7.3 g of magnesium in 100 ml of ether, 7.3 g of hexyltetrachlorodisilanemethane was added. The reaction mixture was heated for 2 hours on a water bath and, after distilling off the ether, for 2 hours on an oil bath at 125°. 3.7 g (yield 55%) of hexyltetraethyldisilanemethane was obtained. B.p. 125–130°/2 mm.

Found, %: C 66.04; 66.03; H 13.28; 13.38
\(\mathrm{C_{15}H_{36}Si_2}\). Calculated, %: C 66.09; H 13.31

2. Preparation of hexylpentabutyldisilanemethane.
To butyllithium, prepared from 14 g of lithium and 140 g of butyl bromide in 400 ml of ether, 35 g of hexylpentachlorodisilanemethane was added. The reaction mixture was heated for 10 hours on a water bath. After distillation over metallic sodium, 30 g (yield 68%) of hexylpentabutyldisilanemethane was obtained. B.p. 179–181°/2 mm.

Found, %: C 73.85; 78.66; H 13.63; 13.68
\(\mathrm{C_{27}H_{60}Si_2}\). Calculated, %: C 73.55; H 13.72

3. Preparation of heptylpentabutyldisilanemethane.
To butyllithium, prepared from 14 g of lithium and 140 g of butyl bromide in 400 ml of ether, 33 g of heptylpentachlorodisilanemethane was added. The reaction mixture was heated on a water bath for 10 hours. After distillation over metal-

metallic sodium, 28 g (yield 64%) of heptylpentabutyldisilanemethane was obtained. B.p. 185–188°/2 mm.

\( \mathrm{C_{28}H_{62}Si_2} \). Found, %: C 73.87; 73.96; H 13.58; 13.53
Calculated, %: C 73.92; H 13.74

4. Preparation of dihexyltetrabutyldisilanemethane. To butyllithium, prepared from 3 g of lithium and 28 g of butyl bromide in 100 ml of ether, 7 g of dihexyltetrachlorodisilanemethane was added.

Table 1

Some silicon hydrocarbons of the disilanemethane and disilaneethane series

The reaction mixture was heated for 12 hours on a water bath. After distillation over metallic sodium, 4.7 g (yield 53%) of dihexyltetrabutyldisilanemethane was obtained. B.p. 199–203°/2 mm.

\( \mathrm{C_{29}H_{64}Si_2} \). Found, %: C 74.21; 74.23; H 14.04; 13.98
Calculated, %: C 74.27; H 13.76

1. Preparation of diheptyltetrabutyldisilanemethane. To butyllithium, prepared from 3 g of lithium and 28 g of butyl bromide in 100 ml of ether, 8 g of diheptyltetrachlorodisilanemethane was added. The reaction mixture was heated for 12 hours on a water bath. After distillation over metallic sodium, 5.4 g (yield 56%) of diheptyltetrabutyldisilanemethane was obtained. B.p. 121–125°/2 mm.

Found, %: C 75.68; 75.69; H 14.09; 14.16
$C_{31}H_{68}Si_2$. Calculated, %: C 74.92; H 13.79

1. Preparation of hexaoctyldisilanemethane. A mixture of 290 g of n-octyl bromide and 35.5 g of hexachlorodisilanemethane in 150 ml of ether was added to 36 g of magnesium and 150 ml of ether. The reaction mixture was heated on a water bath for 3 hours and then, after removal of the ether, for 3 hours on an oil bath at 150–160°. 40 g (yield 40.4%) of hexaoctyldisilanemethane was obtained. B.p. 285–286°/3 mm.

Found, %: C 78.56; 78.36; H 14.01; 13.98
$C_{49}H_{104}Si_2$. Calculated, %: C 78.52; H 13.98

1. Preparation of hexaoctyldisilaneethane. A mixture of 290 g of n-octyl bromide, 36 g of hexachlorodisilaneethane, and 150 ml of ether was added to 36 g of magnesium and 150 ml of ether. The reaction mixture was heated on a water bath for 3 hours and then, after removal of the ether, for another 3 hours on an oil bath at 150–160°. 43 g (yield 44.3%) of hexaoctyldisilaneethane was obtained. B.p. 299–301°/3 mm.

Found, %: C 78.63; 78.72; H 14.05; 13.95
$C_{50}H_{106}Si_2$. Calculated, %: C 78.65; H 13.99

Received
30 XI 1956

REFERENCES

1. A. V. Topchiev, N. S. Nametkin, A. A. Shcherbakova, DAN, 86, 559 (1952).
2. N. S. Nametkin, A. V. Topchiev, F. F. Machus, DAN, 96, 1003 (1954).
3. A. V. Topchiev, N. S. Nametkin, L. S. Povarov, DAN, 97, 99 (1954).
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