Reaction of O,S-bis(trimethylsilyl) (3,5-di-tert-butyl-4-hydroxyphenyl)phosphonodithioate with bis(ethylthio)diphenylgermane [1]

Full text of DOI:10.1023/A:1021606819577

Russian Journal of General Chemistry, Vol. 72, No. 9, 2002, pp. 1485 1486. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 9, 2002,
pp. 1574 1575.
Original Russian Text Copyright
2002 by Nizamov, Popovich, Galimullina, Batyeva, Al’fonsov.
LETTERS
TO THE EDITOR
Reaction of O,S-Bis(trimethylsilyl)
3,5-Di-tert-butyl-4-hydroxyphenyl)phosphonodithioate
(
with Bis(ethylthio)diphenylgermane
I. S. Nizamov, A. E. Popovich, N. G. Galimullina, E. S. Batyeva, and V. A. Al’fonsov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received December 20, 2001
Disilyl phosphonotrithioates which contain two
one of the two S Ge bonds and stops on the stage of
formation of a monosubstituted linear product.
SiMe groups and two S Si bonds have been used for
3
preparing linear and heterocyclic phosphorus-contain-
ing organosulfur compounds by reactions with tetra-
hydrofuran, sulfur chlorides, halogens, and dimethyl
sulfoxide [1]. Recently we prepared O,S-disilyl esters
of arylphosphonodithioic acids by reactions of 2,4-di-
S-(Ethylthio)diphenylgermyl O-trimethylsilyl
3,5-di-tert-butyl-4-hydroxyphenyl)phosphonodi-
thioate (III). To a suspension of 0.8 g of germane II
in 5 ml of anhydrous benzene, 1.0 g of phosphonodi-
thioate I was added dropwise with stirring under
argon at 20 C. The reaction mixture was stirred for
h at 20 C and kept for 1 h at reduced pressure
0.5 mm) and 40 C and then for 1 h in a vacuum
0.03 mm) at 40 C. The volatile fraction was collected
in a liquid-nitrogen trap. The residue, 0.9 g, was
chromatographed on a silica gel column (elution with
benzene) to give 0.6 g (40%) of compound III, Rf
(
5
5
aryl-1,3,2 ,4 -dithiadiphosphetane
2,4-disulfides
with bis(trimethylsilyl)acetamide [2]. Disilyl phos-
phonodithioates containing two different bonds (O Si
and S Si) can be used as intermediate products for
preparing various types of organic phosphorus sulfur
compounds. We found that O,S-bis(trimethylsilyl)
4
(
(
(
(
3,5-ditert-butyl-4-hydroxyphenyl)phosphonodithioate
I) reacts with bis(ethylthio)diphenylgermane (II) at
0
3
2
1
1
.94 (Silufol UV-254, C H ). IR spectrum, , cm :
6 6
2
0 C for 4 h in benzene to give S-(ethylthio)di-
636 w [ (O H)], 3075 w, 3050 w [ (=C H, Ar)],
966 s, 2930 m, 2875 m [ (CH as, s)], [ CH (Si) s],
phenylgermyl O-trimethylsilyl (3,5-di-tert-butyl-4-
hydroxyphenyl)phosphonodithioate (III) and (ethyl-
thio)trimethylsilane (IV).
3
2
585 m, 1485 m [ (C=C, Ar)], 1435 m [ (CH , as)],
3
260 s [ CH (Si) s], 1100 s [ (P Ar)], 860 v.s
3
SEt
[ P O(C)], 695 m [ (P=S)], 652 m [ (C S)], 615 m
1
S
Ar P
I
S
[
(P S)], 465 m [ (GePh )], 408 [ (S Ge)]. H NMR
2
SSiMe3
OSiMe3
S GePh2
OSiMe3
+ (EtS) GePh
Ar P
spectrum, , ppm (J, Hz): 0.33 s [9H, (CH ) SiOP],
3 3
2
2
3
1
(
.31 t (3H, CH CH S, JHH 7.2), 1.56 s [18H,
3 2
II
III
3
CH ) C], 2.97 q (2H, CH CH S, J
7.2), 6.98
3
3
3
2
HH
+
EtSSiMe3,
7
8
6
1
.98 m [10H, (C H ) Ge, 2H, 2,6-H C P].
6 5 2 2 6
P
IV
3.9 ppm. Mass spectrum (70 eV), m/z (I , %):
rel
+
00 (2) [M
Ph]. Found, %: Ge 10.66; P 4.26; S
Ar = HO
.
4.55. C H GeO PS Si. Calculated, %: Ge 10.72;
3
1
45
2
3
P 4.58; S 14.17. M 676.
Hence, under mild conditions, the reaction studied
involves cleavage of the more active S Si bond and
Thiosilane IV, 0.2 g (67%), was collected in the
trap, n2 1.4522. H NMR spectrum, , ppm (J, Hz):
0
1
D
1
070-3632/02/7209-1485$27.00 2002 MAIK Nauka/Interperiodica

1486
NIZAMOV et al.
3
0
7
(
.30 s [9H, (CH ) Si], 1.30 t (3H, CH CH S, J
spectra were obtained on a Hitachi M-80B GC MS
system.
3
3
3
2
HH
3
.5); 2.54 q (2H, CH CH S, J 7.5). Mass spectrum
70 eV), m/z (I , %): 135 (2) [M + 1] (calculated M:
3
2
HH
+
rel
REFERENCES
2
0
1
34.2). Published data [3]: n 1.4512.
D
1
. Hahn, J. and Nataniel, T., Z. Anorg. Allg. Chem., 1986,
vol. 543, no. 12, pp. 7 21.
The IR spectra were recorded on a UR-20 spectro-
meter for thin layers between KBr plates. The H
NMR spectra were obtained on a Varian T-60 spec-
trometer (60 MHz) in CCl solutions against internal
CH Cl . The P NMR spectra were measured on a
Bruker MSL-400 spectrometer (162 MHz) for C H6
solutions against 85% phosphoric acid. The mass
1
2. Nizamov, I.S., Popovich, A.E., Batyeva, E.S., and
Alfonsov, V.A., Heteroatom. Chem., 2000, vol. 11,
no. 4, pp. 276 280.
3. Bazant, V., Chavalovsky, V., and Rathousky, J.,
Organosilicon Compounds, Prague: Czech. Acad. Sci.,
1965, vol 2 (1).
4
3
1
2
2
6
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 9 2002