ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 2, p. 338. + Pleiades Publishing, Ltd., 2007.
Original Russian Text + M.G. Voronkov, R.G. Mirskov, S.N. Adamovich, 2007, published in Zhurnal Prikladnoi Khimii, 2007, Vol. 80, No. 2, p. 339.
Synthesis of High-Purity Trialkylgermanethiols
M. G. Voronkov, R. G. Mirskov, and S. N. Adamovich
Favorksii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received December 26, 2006
Abstract-A procedure was developed for preparing high-purity trialkylgermanethiols by the reaction of
hexaalkyldigermoxanes with hydrogen sulfide.
GeSH (I) (R = Alk) are
promising chemicals for fine organometallic synthesis
and precursors for plasmochemical deposition of thin
dielectric layers containing germanium and sulfur atoms.
Henry and Davidson  prepared triarylgermane-
thiols by reacting triarylhalogermanes with hydro-
gen sulfide in the presence of pyridine. However, this
procedure appeared to be unsuitable for preparing
the related alkyl compounds I.
Vyazankin et al.  prepared previously unknown
trialkylgermanethiols I in 49.5% yield by heating tri-
alkylgermanes with sulfur at 140oC for 4 h in an inert
atmosphere. The drawbacks of their procedure are
the relatively low yield of I, difficult synthesis of
the starting trialkylgermanes, and use of high temper-
atures and inert gases.
For applications in microelectronics, compounds
I of ultrahigh purity should be prepared. To this end,
we developed a procedure for preparing high-purity
trialkylgermanethiols in high yield by the reactions
of hexaalkyldigermoxanes (which are readily prepared
by hydrolysis of trialkylhalogermanes) with hydrogen
sulfide at room temperature:
S 6 2R
GeSH + H
where R = C
Triethylgermanethiol. Hydrogen sulfide was bub-
bled for 2 h at 20oC through a flask containing 16.8 g
(0.05 mol) of hexaethyldigermoxane, until the mixture
became turbid. After a 1-h pause, hydrogen sulfide
was bubbled for an additional 0.5 h. In the process,
the mixture spontaneously warmed up to 50oC and
then cooled to room temperature. By vacuum distilla-
tion we isolated 15.4 g (80%) of triethylgermanethiol,
bp 473 48oC (6 mm Hg), d
= 1.1249, n
Published data : bp 86oC (35 mm Hg), d
Found, %: C 37.44, H 8.45, Ge 37.57, S 16.52.
Calculated, %: C 37.40, H 8.40, Ge 37.60, S 16.60.
H NMR (CDCl
, HMDS), d, ppm: 1.81 (CH
), 3.6 (SH); IR, n,cm
: 2555 (n
), 408 (n
Tributylgermanethiol was prepared similarly from
10 g (0.02 mol) of hexabutyldigermoxane; yield 7.2 g
(65%), bp 1043106oC (3 mm Hg),
Found, %: S 11.37.
Calculated, %: S 11.57.
According to GLC analysis, the products purified
by vacuum distillation on a quartz column contained
no traces of organic impurities. The content of metals
(Na, K, Ca, Fe, Ni, Co, etc.), according to atomic
absorption analysis, did not exceed 10
for each metal.
A procedure was developed for preparing high-
purity trialkylgermanethiols for micro- and optoelec-
tronics technology in 65380% yields by reactions of
accessible hexaalkylgermoxanes with hydrogen sulfide
for 3 h at room temperature, followed by isolation of
the products by fractional distillation in a vacuum.
The study was supported by the Grant Council
of the President of the Russian Federation (NSh-
1. Henry, M.C. and Davidson, W.E., Can. J. Chem., 1963,
vol. 41, p. 1276.
2. Vyazankin, N.S., Bochkarev, M.N., and Sanina, L.P.,
Zh. Obshch. Khim., 1966, vol. 36, p. 1154.