1404
KIRILIN et al.
a
4Me2NNH2 + ClSi(Me)2CH2CH2Si(Me)2Cl
CH2Si(Me)2NHNMe2
XI
CH2Si(Me)2NHNMe2
b
2Me2NN(SiMe3)2 + XI
XII
ClSi(Me)2CH2CH2Si(Me)2
ClSi(Me)2CH2CH2Si(Me)2
b
Me2NN(SiMe3)2 + XI
NNMe2
XIII
CH2Si(Me)2NCO
b
Me3SiNCO + XI
CH2Si(Me)2NCO
IV
3 mm, packing SE-30 on Chromaton N-AW, carrier
gas helium).
in a vacuum. Ether, 200 ml, was distilled off from the
mother liquor, the residue was cooled, and the pre-
cipitate was filtered off to obtain an additional crop
of the reaction product. Total yield 15.93 g (94%),
The IR spectra were obtained on a Specord IR-75
instrument in thin films (liquids) and mineral oil
(solids). The 1H NMR spectra were recorded on a
Bruker WP-8 instrument (80 MHz), solvent and
internal reference CDCl3.
1
mp 90 92 C. H NMR spectrum, , ppm: 1.43 s (6H,
NCH3), 2.29 t (6H, NCH2), 3.59 t (6H, OCH2,), 4.2 s
(2H, SiCH2). Found, %: C 43.22; H 8.56; N 16.49; Si
10.89. C9H21N3O3Si. Calculated, %: C 43.70; H 8.56;
N 16.99; Si 11.35.
2-{[Diethoxy(methyl)silyl]methyl}-1,1-dimethyl-
hydrazine (Va). A mixture of 65.60 g of (chloro-
methyl)(diethoxy)methylsilane and 43.15 g of 1,1-di-
methylhydrazine was heated for 42 h at 60 C. Frac-
tionation gave 23.26 g (31.4%) of compound Va, bp
1,3-Bis(2-chloroethenyl)-1,1,3,3-tetramethyldi-
siloxane (IXa). A mixture of 23.26 g (2-chloro-
ethenyl)(ethoxy)dimethylsilane (cis/trans ratio 3:1)
and 16.97 g of 1,1-dimethylhydrazine was heated with
a distillation head until ethanol no longer distilled,
after which it was fractionated to isolate 9.04 g (75%)
of compound IXa (cis/trans ratio was not estimated),
118 120 C (3 mm Hg), n2D0 1.4153. H NMR spec-
1
trum, , ppm: 0.01 s (3H, SiCH3), 2.28 s (6H, NCH3),
2.76 s (2H, SiCH2). Found, %: C 46.61; H 10.84; Si
13.72. C8H22N2O2Si. Calculated, %: C 46.57; H 10.75;
Si 13.60.
bp 70 C (2 mm) n2D0 1.4515. IR spectrum, , cm :
1
1
1040 (SiOSi); 1560 and 3040 (C=C). H NMR spec-
trum, , ppm: 0.35 s (12H, SiCH3), 6.2 d and 6.5 d
(2H, CH=CH). Found, %: C 37.53; H 6.17; Cl 27.62.
C8H16Cl2OSi2. Calculated, %: C 37.64; H 6.32; Cl
27.77.
Compounds Vb and Vc were obtained in a similar
way (Table 1).
2-[(2,2-Dimethylhydrazino)methyl]-2,5,6-tri-
methyl-1,3,4,7,2-dioxadiazasilepine (VI). A mixture
of 4.53 g of compound Va, 2.55 g of butane-2,3-dione
dioxime, and a catalytic amount of lithium was heated
with a distillation head until ethanol no longer dis-
tilled. The reaction mixture was subjected a vacuum
(15 mm Hg) to obtain 4.02 g (79.5%) of compound
Compounds IXb IXd were obtained in a similar
way (Table 2).
2,4,4,7,7,9-Hexamethyl-2,3,8,9-tetraza-4,7-di-
siladecane (XII). a. A mixture of 30 g of 1,1-di-
methylhydrazine and 26.86 g of chloro{2-[chloro(di-
methyl)silyl]ethyl}dimethylsilane (XI) was heated for
41 h at 60 C and fractionated to isolate 22.28 g (68%)
of compound XII, bp 111 C, n2D0 1.4561. IR spectrum,
1
VI as a viscous oil. IR spectrum, , cm : 3350 (NH),
1600 (C=N). Found, %: C 41.47; H 7.91; Si 11.11.
C8H18N4O2Si. Calculated, %: C 41.69; H 7.87; Si
12.19.
1
1
, cm : 3110 (NH). H NMR spectrum, , ppm:
0.35 s (12H, SiCH3), 0.86 t (4H, SiCH2CH2), 2.62 s
(6H, NCH3). Found, %: C 45.01; H 11.31. C10H30N4
Si2. Calculated, %: C 45.75; H 11.52.
(2,2-Dimethylhydrazino)methylsilatrane (VII).
1,1-Dimethyl-2-(triethoxylsilyl)hydrazine (Vc),
16.19 g, was added dropwise at 80 C to a mixture of
10.23 g of triethanolamine and 2 g of freshly prepared
sodium methylate. The reaction mixture was refluxed
for 3 ½. After 12 h, the crystals that formed were
filtered off, washed with ether (2 100 ml), and dried
b. A mixture of 10.93 g of compound XI and
13.44 g of 1,1-dimethyl-2-(trimethylsilyl)hydrazine
was heated with a distillation head until chlorotri-
methylsilane no longer distilled. Fractionation gave
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 9 2005
Kirilin
