Synthesis of high-purity trialkylgermanethiols
Voronkov, M.; Mirskov, R.; Adamovich, S.
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. BRIEF COMMUNICATIONS 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. DOI: 10.1134/S1070427207020334 Trialkylgermanethiols R GeSH (I) (R = Alk) are Found, %: C 37.44, H 8.45, Ge 37.57, S 16.52. promising chemicals for fine organometallic synthesis C H GeS. 6 16 and precursors for plasmochemical deposition of thin Calculated, %: C 37.40, H 8.40, Ge 37.60, S 16.60. dielectric layers containing germanium and sulfur atoms. H NMR (CDCl , HMDS), , ppm: 1.81 (CH ), 2.02 3 3 Henry and Davidson  prepared triarylgermane- (CH ), 3.6 (SH); IR, ,cm : 2555 ( ), 408 ( ). 2 S H Ge S thiols by reacting triarylhalogermanes with hydro- Tributylgermanethiol was prepared similarly from gen sulfide in the presence of pyridine. However, this 10 g (0.02 mol) of hexabutyldigermoxane; yield 7.2 g procedure appeared to be unsuitable for preparing (65%), bp 104 106 C (3 mm Hg), d = 1.0219, n = 20 D the related alkyl compounds I. 1.4810. Vyazankin et al.  prepared previously unknown Found, %: S 11.37. trialkylgermanethiols I in 49.5% yield by heating tri- C H GeS. 12 28 alkylgermanes with sulfur at 140 C for 4 h in an inert Calculated, %: S 11.57. atmosphere. The drawbacks of their procedure are According to GLC analysis, the products purified the relatively low yield of I, difficult synthesis of by vacuum distillation on a quartz column contained the starting trialkylgermanes, and use of high temper- no traces of organic impurities. The content of metals atures and inert gases. (Na, K, Ca, Fe, Ni, Co, etc.), according to atomic 5 6 For applications in microelectronics, compounds absorption analysis, did not exceed 10 10 wt % I of ultrahigh purity should be prepared. To this end, for each metal. we developed a procedure for preparing high-purity CONCLUSION trialkylgermanethiols in high yield by the reactions of hexaalkyldigermoxanes (which are readily prepared A procedure was developed for preparing high- by hydrolysis of trialkylhalogermanes) with hydrogen purity trialkylgermanethiols for micro- and optoelec- sulfide at room temperature: tronics technology in 65 80% yields by reactions of accessible hexaalkylgermoxanes with hydrogen sulfide R GeOGeR +2H S 2R GeSH + H O, 3 3 2 3 2 for 3 h at room temperature, followed by isolation of the products by fractional distillation in a vacuum. where R = C H or C H . 2 5 4 9 Triethylgermanethiol. Hydrogen sulfide was bub- ACKNOWLEDGMENTS bled for 2 h at 20 C through a flask containing 16.8 g (0.05 mol) of hexaethyldigermoxane, until the mixture The study was supported by the Grant Council of the President of the Russian Federation (NSh- became turbid. After a 1-h pause, hydrogen sulfide 4575.2006.3). was bubbled for an additional 0.5 h. In the process, the mixture spontaneously warmed up to 50 C and REFERENCES then cooled to room temperature. By vacuum distilla- tion we isolated 15.4 g (80%) of triethylgermanethiol, 1. Henry, M.C. and Davidson, W.E., Can. J. Chem., 1963, 4 20 bp 47 48 C (6 mm Hg), d = 1.1249, n = 1.4900. vol. 41, p. 1276. 20 D Published data : bp 86 C (35 mm Hg), d = 2. Vyazankin, N.S., Bochkarev, M.N., and Sanina, L.P., 1.1270, n = 1.4852. Zh. Obshch. Khim., 1966, vol. 36, p. 1154.
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