TRANSETHERIFICATION OF ORGANOSILICON AMINES
1387
1
Table 5. Rate constants (l mol 1 s ) of the first and
second stages of transetherification of amines with tri-
methylsilanol at 70 C
stirred at 20 C until amine Ib had been consumed
completely. Vacuum distillation gave 267.4 g of
compound V, bp 109 111 C (1 mm).
3-[3-N-(2-Aminoethyl)aminopropyl]-3-methoxy-
1,1,1,5,5,5-hexamethyltrisiloxane (VI). A mixture
of 222 g of compound Ib and 185 g of Me3SiOH was
refluxed until silane V had been consumed completely.
Vacuum distillation gave 312.7 g of compound VI,
bp 110 115 C (1 mm).
Comp. no.
k1 104
k2 104
Ib
Ic
VIII
6.166
0.630
10.000
0.043
0.080
0.450
[3-N-(2-Aminoethyl)aminopropyl]tris(trimethyl-
siloxy)silane (VII). A mixture of 222 g of compound
Ib and 540 g of Me3SiOH was refluxed until com-
pound VI had been consumed completely. Vacuum
distillation gave 271.3 g of compound VII, bp 127
130 C (1 mm).
methoxy or ethoxy groups by trimethylsiloxy or
2-ethoxyethoxy (Fig. 4). On complete trimethylsiloxy
substituion, the silicon signal shifts upfield by 23.71
and 20.59 ppm for methoxy and ethoxy groups,
respectively. On substitution of methoxy groups in Ib
by 2-ethoxyethoxy, the difference is 2.8 ppm
(Table 1).
ACKNOWLEDGMENTS
EXPERIMENTAL
The work was financially supported by the Interna-
tional Scientific and Technological Center (grant
no. 1891).
The H and 29Si NMR spectra were registered in
1
CDCl3 on a Bruker AM-360 instrument at 360 and
80 MHz.
REFERENCES
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1-[3-N-(2-Aminoethyl)aminopropyl]-1,1-di-
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ppm
40
Si,
3
45
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2
50
55
1
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60
65
70
0
1
2
3
n
Fig. 4. Plot of silicon chemical shift
vs. substitution
Si
degree for (1) trimethylsilylation of compound Ic,
(2) trimethylsilylation of compound Ib, and (3) trans-
etherification of compound Ib with Cellosolve.
n
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 9 2003