Synthesis and thermal stability of N-(chlorodimethylgermylmethyl)-N-methyl-O-(trimethylsilyl)salicylamide

Full text of DOI:10.1023/A:1013210103909

Russian Journal of General Chemistry, Vol. 71, No. 8, 2001, pp. 1323 1324. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 8, 2001,
pp. 1401 1402.
Original Russian Text Copyright
2001 by Bylikin, Kramarova, Shipov, Negrebetskii, Baukov.
LETTERS
TO THE EDITOR
Synthesis and Thermal Stability
of N-(Chlorodimethylgermylmethyl)-N-methyl-
O-(trimethylsilyl)salicylamide
S. Yu. Bylikin, E. P. Kramarova, A. G. Shipov, Vad. V. Negrebetskii, and Yu. I. Baukov
Russian State Medical University, Moscow, Russia
Received November 15, 2000
N,O-Bis(trimethylsilyl)-N-methylsalicylamide (I)
reacts with chloro(chloromethyl)dimethylsilane under
mild conditions with liberation of chlorotrimethyl-
silane and intermediate formation of a five-coordinate
silicon compound, N-(chlorodimethylsilylmethyl)-N-
methyl-O-(trimethylsilyl)salicylamide. On fractiona-
tion or standing at room temperature the latter under-
goes intramolecular cyclization to 2,2,4-trimethyl-1-
oxa-4-aza-2-silabenzocycloheptan-5-one with libera-
tion of chlorotrimethylsilane [1, 2]. By contrast,
chloro(chloromethyl)dimethylgermane (II) reacts with
compound I at room temperature within 1.5 2 h in
pentane to give, first, intermediate O-alkylation
product III whose spectral characteristics are close to
those of the products of syntheses on the basis of
amides and lactams [3]. Thus, the IR spectrum of
compound III shows a strong imidate absorption at
and OCH2Ge (4.08 ppm) groups. After standing for
some days at room temperature compound III iso-
merized to N-germylmethylation product IV. This
conversion is accompanied by disappearance in the IR
1
spectrum of the absorption band at 1678 cm and
1
appearance of absorption bands at 1597 and 1500 cm
due to the five-memebered O Ge chelate fragment
[3]. The half-conversion period of compound III to
IV in the reaction mixture was ca. 3 days at room
temperature. No further conversion of compound IV
into a germanium-containing heterocycle with chlro-
trimethylsilane liberation occurred even on vacuum
fractionation at a temperature above 200 C. This
points to a strongly reduced reactivity of five-coor-
dinate germanium chlorides compared with their
silicon analogs toward trimethylsilyl phenol ethers
[4], apparently, on account of a weaker O M co-
ordination interaction in germanium analogs [5].
1
1678 cm , and the 1H NMR spectrum contains
signals of the Me2Ge (0.97 ppm), MeN (2.96 ppm),
O
GeMe2Cl
O
O
GeMe2Cl
NMe
ClCH2GeMe2Cl
N(Me)SiMe3
N
II
Me
OSiMe3
Me3SiCl
OSiMe3
III
OSiMe3
I
IV
N-(Chlorodimethylgermylmethyl)-N-methyl-O-
(trimethylsilyl)salicylamide (IV). a. A solution of
0.94 g of ClCH2GeMe2Cl in 2 ml of pentane was
added to a solution of 1.37 g of compound I in 3 ml
of pentane. The reaction mixture was stirred for 1.5 h
at room temperature. In the IR spectrum of the reac-
tion mixture we observed gradual disappearance of
the absorption band of the starting compound at
1
1636 cm and appearance of a strong absorption band
1
at 1678 cm due to O-germylation product III.
1
Further on the band at 1678 cm disappeared and
1
bands at 1598 and 1520 cm appeared, belonging to
N-germylation product IV.
1070-3632/01/7108-1323$25.00 2001 MAIK Nauka/Interperiodica

1324
BYLIKIN et al.
b. A distillation flask was charged with 2.6 ml of
eva, E.A., Zaitseva, G.S., Sergeev, V.N., and Bau-
kov, Yu.I., Zh. Obshch. Khim., 1993, vol. 63, no. 5,
pp. 1195 1196.
ClCH2GeMe2Cl and 5.50 g of compound I. At 90
155 C, Me3SiCl (1.09 g) was distilled off. The residue
was fractionated to obtain 4.16 g (85%) of compound
IV, bp 215 217 C (10 mm). IR spectrum (CHCl3), ,
2. Kurochka, A.V., Afanasova, O.A., Losev, A.S., Ma-
maeva, E.A., Bylikin, S.Yu., Negrebetsky, Vad.V.,
Kramarova, E.P., Shipov, A.G., and Baukov, Yu.I.,
Metal-Based Drugs, 1998, vol. 5, no. 1, pp. 25 33.
1
1
cm : 1598 s, 1520 w. H NMR spectrum (CDCl3), ,
ppm: 0.08 s (9H, SiMe3), 0.77 s (6H, GeMe2),
2.88 s + s (5H, NCH2C + NCH2Ge), 6.6 7.3 m (4H,
C6H4). Found, %: C 45.35; H 6.12. C14H24ClGeNO2Si.
Calculated, %: C 44.88; H 6.45.
3. Kalikhman, I.D., Albanov, A.I., Bannikova, O.B.,
Belousova, L.I., Pestunovich, S.V., Voronkov, M.G.,
Pestunovich, V.A., Macharashvili, A.A., Shklover, V.E.,
Struchkov, Yu.T., Khaustova, T.I., Zueva, G.Ya.,
Kramarova, E.P., Shipov, A.G., Oleneva, G.I., and
Baukov, Yu.I., Metalloorg. Khim., 1989, vol. 2, no. 3,
pp. 637 643.
The IR spectra of CHCl3 solutions were taken on a
1
Specord IR-75 instrument in KBr. The H NMR spec-
tra were obtained on a Varian XL-400 spectrometer
(400.1 MHz) in the pulse mode with subsequent
2
Fourier transform and H stabilization of resonance
conditions. The chemical shifts were measured
relative to internal TMS.
4. Artamkina, O.B., Kramarova, E.P., Shipov, A.G.,
Baukov, Yu.I., Macharashvili, A.A., Ovchinni-
kov, Yu.E., and Struchkov, Yu.T., Zh. Obshch. Khim.,
1993, vol. 63, no. 10, pp. 2289 2300.
ACKNOWLEDGMENTS
5. Baukov, Yu.I., Shipov, A.G., Ovchinnikov, Yu.E., and
Struchkov, Yu.T., Izv. Ross. Akad. Nauk, Ser. Khim.,
1994, no. 6, pp. 982 993; Bylikin, S.Yu., Pogo-
zhikh, S.A., Khrustalev, V.N., Negrebetskii, Vad.V.,
Shipov, A.G., Ovchinnikov, Yu.E., and Baukov, Yu.I.,
Izv. Ross. Akad. Nauk, Ser. Khim., 2000, no. 1,
pp. 137 144.
The work was financially supported by the Russian
Foundation for Basic Research (project no. 98-03-
32999).
REFERENCES
1. Shipov, A.G., Kramarova, E.P., Bylikin, S.Yu., Mama-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 8 2001