Russian Journal of General Chemistry, Vol. 71, No. 3, 2001, p. 485. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 3, 2001, p. 522.
Original Russian Text Copyright
2001 by Nizamov, Batyeva, Nizamov, Al’fonsov.
LETTERS
TO THE EDITOR
Reaction of Lawesson’s Reagent
with Dibutylbis(ethylthio)stannane
I. S. Nizamov, E. S. Batyeva, I. D. Nizamov, and V. A. Al’fonsov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received February 23, 2000
We previously studied the reactivity of 1,3,2 ,4 -
dithiadiphosphetane 2,4-disulfides toward geminal
bis(alkylthio) derivatives of Group IV elements using
the reaction with thioacetals as an example [1]. Reac-
tions of bis(alkylthio)stannanes containing two S Sn
bonds with 1,3,2 ,4 -dithiadiphosphetane 2,4-di-
sulfides were not examined.
thermoelement temperature 150 C (0.06 mm), nD20
1.5728. IR spectrum, , cm : 3070 w, 3030 sh
5
5
1
(C Harom); 2963 s, 2930 s, 2875 m, 2860 m (C H in
CH3 and CH2, sym. and asym.); 1590 s, 1500 s,
1460 m (C Carom), 1260 s ( , CH2); 675 m, very
broad (P S); 623 m (C C); 545 m, br (Sn S);
5
5
1
515 m (P S). H NMR spectrum, , ppm (J, Hz):
0.73 2.05 m (27H, CH3CH2S, CH3CH2CH2CH2Sn),
We have found that 2,4-bis(4-methoxyphenyl)-
2.33 3.07 m (4H, CH3 1H2S), 3.83 s (3H, CH3O),
5
5
1,3,2 ,4 -dithiadiphosphetane 2,4-disulfide (I,
Lawesson’s reagent) reacts with dibutylbis(ethylthio)-
stannane (II) (10 C, 4 h), yielding dibutyl(ethylthio)-
stannyl ethyl 4-methoxyphenylphosphonotrithioate
(III). Thus, the reaction occurs under mild conditions
and involves only one Sn S bond.
3
4
6.87 d.d (2H, m-H, JHH3 = 9.0, JPH = 3.0), 8.06 d.d
(2H, o-H, JHH = 9.0, JPH = 15.0). 31P NMR spec-
3
trum:
77.0 ppm. Found, %: P 5.56; Sn 21.31.
P
C19H35OPS4Sn. Calculated, %: P 5.31; Sn 21.08.
The IR spectrum was taken on a UR-20 spectrom-
1
eter. The H spectrum was recorded on a Varian T-60
SEt
instrument (60 MHz) in CDCl3 containing HMDS as
internal reference. The 31P NMR spectrum was
obtained on a Bruker MSL-400 spectrometer at
162 MHz using benzene as solvent and 85% H3PO4
as reference.
S
S
S SnBu2
SEt
S
S
Ar P
2
Ar P
P Ar + 2EtS SnBu2
S
I
II
III
Ar = 4-MeOC6H4.
ACKNOWLEDGMENTS
Dibutyl(ethylthio)stannyl ethyl 4-methoxy-
phenylphosphonotrithioate (III). To a solution of
2.0 g of dithiostannane II in 10 ml of dry benzene,
stirred at 10 C under dry argon, we added in portions
1.1 g of Lawesson’s reagent (I). The mixture was
stirred for 4 h at 10 C and filtered. The filtrate was
evacuated under a residual presure of 0.5 and 0.04 mm
for 2 h at 40 C. The residue was subjected to film
distillation to isolate 1.5 g (50%) of product III,
This study was financially supported by the Rus-
sian Foundation for Basic Research (project no. 95-
03-09739a).
REFERENCE
1. Nizamov, I.S., Al’metkina, L.A., Batyeva, E.S.,
Al’fonsov, V.A., and Pudovik, A.N., Phosphorus,
Sulfur, Silicon, 1992, vol. 72, nos. 1 4, pp. 229 236.
1070-3632/01/7103-0485$25.00 2001 MAIK Nauka/Interperiodica