CHEMISTRY

N. G. DZHURINSKAYA, V. F. MIRONOV
and Corresponding Member of the Academy of Sciences of the USSR A. D. PETROV

ADDITION OF GERMANIUM HYDRIDES TO UNSATURATED COMPOUNDS

In previous papers \((^{1,2})\) we established for the first time that \(\mathrm{HGeCl_3}\) readily adds, without any activation and without catalysts, to practically any unsaturated compounds

\[ \mathrm{Cl_3GeH} + \begin{array}{c} \backslash \\[-0.7em] \mathrm{C}=\mathrm{C} \\[-0.7em] / \quad \backslash \end{array} \quad \mathrm{Cl_3GeC{-}CH}. \]

We therefore came to the conclusion that \(\mathrm{HGeCl_3}\) is more reactive in this reaction than \(\mathrm{HSiCl_3}\), whose addition takes place only in the presence of catalysts and under more severe conditions.

In the present investigation we carried out the addition of \(\mathrm{HGeCl_3}\) to a number of further unsaturated compounds (see Table 1). The preparation by this method, for example, of \(n\)-\(\mathrm{C_3H_7GeCl_3}\), is considerably more convenient than the “direct” or organomagnesium syntheses of this compound \((^3)\). Trichlorogermane adds vigorously to cyclopentadiene, whereas we were unable to carry out the addition of trichlorosilane to the latter even in the presence of \(\mathrm{H_2PtCl_6}\) and on boiling.

Table 1*

* All the compounds listed show, on titration \((^2)\), the theoretical amount of chlorine.
** Titrates four chlorine atoms.

To assess the relative reactivity of hydrides other than \(\mathrm{Cl_3MH}\), we obtained \((\mathrm{C_2H_5})_3\mathrm{MH}\) \((^{4,5})\) (where \(M=\mathrm{Si}, \mathrm{Ge}\), and \(\mathrm{Sn}\)) by reducing the corresponding \((\mathrm{C_2H_5})_3\mathrm{MHal}\) with \(\mathrm{LiAlH_4}\).

An attempt to synthesize \((\mathrm{C_2H_5})_3\mathrm{GeH}\) by the action of \(\mathrm{C_2H_5MgBr}\) on \(\mathrm{Cl_3GeH}\) was unsuccessful; mainly \((\mathrm{C_2H_5})_4\mathrm{Ge}\) was formed, whereas \((\mathrm{C_2H_5})_3\mathrm{SiH}\) is obtained by an analogous route in high yield.

It is interesting to note that treatment of \((\mathrm{C_2H_5})_3\mathrm{MH}\) with a one-normal alcoholic solution of KOH at 20° in a Zerevitinov apparatus led to quantitative evolution of hydrogen only with the silicon and tin hydrides (the latter evolved \(\mathrm{H_2}\) more rapidly). Triethylgermane did not evolve hydrogen at all, even when the temperature was raised to 80°. At the same time, there are data \((^6)\) that \(\mathrm{SnH_4}\) and \(\mathrm{GeH_4}\), in contrast to \(\mathrm{SiH_4}\), do not react with wat-

alkali. All three hydrides \((\mathrm{C_2H_5})_3\mathrm{MH}\) add to propargyl alcohol and to acrolein. Triethylstannane adds to these compounds extremely vigorously, and we were unable to isolate any individual substances: only polymers are formed. Triethylgermane, on the contrary, adds to propargyl alcohol only with a catalyst \((\mathrm{H_2PtCl_6})\), i.e., in the same way as \((\mathrm{C_2H_5})_3\mathrm{SiH}\) \((^7)\):

\[ (\mathrm{C_2H_5})_3\mathrm{GeH}+\mathrm{HC}\equiv\mathrm{CH_2OH} \to (\mathrm{C_2H_5})_3\mathrm{GeCH}=\mathrm{CHCH_2OH}. \]

A difference between \((\mathrm{C_2H_5})_3\mathrm{GeH}\) and \((\mathrm{C_2H_5})_3\mathrm{SiH}\) could be established only in their reaction with allyl alcohol. Whereas triethylsilane forms exclusively allyloxytriethylsilane \((^8)\):

\[ \mathrm{CH_2}=\mathrm{CHCH_2OH}+(\mathrm{C_2H_5})_3\mathrm{SiH} \to \mathrm{CH_2}=\mathrm{CHCH_2OSi}(\mathrm{C_2H_5})_3+\mathrm{H_2}, \]

\[ (\mathrm{C_2H_5})_3\mathrm{GeH} \]
adds already at the multiple bond:

\[ \mathrm{CH_2}=\mathrm{CHCH_2OH}+(\mathrm{C_2H_5})_3\mathrm{GeH} \to (\mathrm{C_2H_5})_3\mathrm{GeCH_2CH_2CH_2OH}. \]

The addition of these two hydrides to acrolein also proceeds at different reaction centers. Triethylsilane, as is known \((^9)\), adds in the 1,4-position:

\[ (\mathrm{C_2H_5})_3\mathrm{SiH} + \mathrm{CH_2}=\mathrm{CHC} \begin{matrix} \mathrm{O}\\[-2pt] \|\\[-2pt] \mathrm{H} \end{matrix} \to (\mathrm{C_2H_5})_3\mathrm{SiOCH}=\mathrm{CHCH_3}. \]

We repeated the experiment of Lesbre and Satgé \((^{10})\) and found that triethylgermane adds to acrolein with considerable difficulty, indeed apparently forming the corresponding aldehyde (poor analysis, but the IR spectra indicate the presence of an aldehyde group).

We carried out the synthesis of other organogermanium carbo-substituted alcohols according to the following schemes:

\[ \mathrm{CH_2}=\mathrm{CH}(\mathrm{CH_2})_n\mathrm{O_2CCH_3} \xrightarrow{\mathrm{HGeCl_3}} \mathrm{Cl_3GeCH_2CH_2}(\mathrm{CH_2})_n\mathrm{O_2CCH_3} \xrightarrow{\mathrm{CH_3MgCl}} \]

\[ \to (\mathrm{CH_3})_3\mathrm{Ge}(\mathrm{CH_2})_n\mathrm{CH_2CH_2OH} \qquad (\text{where } n=0,1); \]

\[ \mathrm{CH}\equiv\mathrm{CCH_2OH} \xrightarrow{\mathrm{RMgX}} \mathrm{XMgC}\equiv\mathrm{CCH_2OMgX} \xrightarrow[\mathrm{H_2O}]{(\mathrm{C_2H_5})_3\mathrm{GeBr}} (\mathrm{C_2H_5})_3\mathrm{GeC}\equiv\mathrm{CCH_2OH}. \]

And, finally, starting from allyltrimethylgermane, we obtained the first representative of organogermanium mercaptans, which, as it turned out, is readily cyanoethylated.

\[ (\mathrm{CH_3})_3\mathrm{GeCH_2CH}=\mathrm{CH_2} \xrightarrow{\mathrm{HSOCCH_3}} (\mathrm{CH_3})_3\mathrm{GeCH_2CH_2CH_2SOCCH_3} \xrightarrow{\mathrm{NaOH}} \]

\[ \to (\mathrm{CH_3})_3\mathrm{GeCH_2CH_2CH_2SH} \xrightarrow{\mathrm{CH_2}=\mathrm{CHCN}} (\mathrm{CH_3})_3\mathrm{GeCH_2CH_2CH_2SCH_2CH_2CN}. \]

The properties of the compounds obtained are presented in Table 2.
The Raman spectra (k. r. s.) were recorded by L. A. Leites.

Experimental part

Propyltrichlorogermane \(n\)-\(\mathrm{C_3H_7GeCl_3}\). A stream of propylene was passed for 4 h through 116 g of trichlorogermane (with \(\sim 30\%\ \mathrm{GeCl_4}\)) \((^1)\). Self-heating to \(\sim 50^\circ\) was observed. After cooling, the contents of the flask were heated on a hot plate at \(\sim 90^\circ\) for 2 h under a continuous stream of propylene. Distillation on a column gave 38 g of \(\mathrm{GeCl_4}\), b.p. \(83^\circ\), and 81 g of propyltrichlorogermane, b.p. \(163.5^\circ\). Yield 85% based on pure trichlorogermane.

Raman spectrum, \(\Delta\nu\) in \(\mathrm{cm^{-1}}\): 147(9sh), 173(9), 190(0), 255(5sh), 303(7), 342(2), 384(8), 419(10), 429(7sh), 589(6), 663(8), 756(0), 801(0), 877(2), 897(0), 1029(5), 1071(8), 1105(1), 1143(1sh), 1170(1), 1190(7), 1211(2), 1248(0), 1300(1d), 1343(2), 1389(1), 1410(2), 1452(6sh), 1481(1), 2875(9), 2914(9), 2937(9), 2971(7).

β-(Trichlorogermyl) ethyl acetate Cl₃GeCH₂CH₂O₂CCH₃. To 27 g of vinyl acetate, with stirring, 54 g of trichlorogermane (1) was added at such a rate that the temperature of the mixture did not rise above 70°. Vacuum distillation gave 32 g of Cl₃GeCH₂CH₂O₂CCH₃, b.p. 97–98° at 15 mm. Yield 57%.

The remaining organogermanium compounds listed in Table 1 were obtained analogously.

β-(Trimethylgermyl)ethanol (CH₃)₃GeCH₂CH₂OH. To CH₃MgCl, prepared from 35 g of Mg in 0.6 l of ether, 48 g of β-(trichlorogermyl)ethyl acetate was added. After boiling for one hour, the contents of the flask were decomposed with 10% HCl. The ether layer and ether extracts from the aqueous layer were dried over Na₂SO₄. Vacuum distillation gave 23 g of (CH₃)₃GeCH₂CH₂OH with b.p. 48° at 10 mm.

IR spectrum, Δν in cm⁻¹: 150(2 sh), 195(7 sh), 281(2 sh), 559(10), 604(8 sh), 885(3), 1051(1), 1086(0), 1242(4 sh), 1416(1 sh), 1461(2 sh), 2864(1 sh), 2915(9 sh), 2975(9 sh).

γ-(Trimethylgermyl)propanol was obtained analogously from γ-(trichlorogermyl)propyl acetate (1).

γ-(Triethylgermyl)propanol (C₂H₅)₃GeCH₂CH₂CH₂OH. A mixture consisting of 18 g of allyl alcohol, 20 g of (C₂H₅)₃GeH, and two drops of 0.1 N H₂PtCl₆·6H₂O solution in isopropyl alcohol was heated at ~90° for 4 h. Vacuum distillation gave 24 g of (C₂H₅)₃GeCH₂CH₂CH₂OH, b.p. 89–90° at 3 mm. Yield 73%.

γ-(Triethylgermyl)allyl alcohol (C₂H₅)₃GeCH=CHCH₂OH. Under the conditions of the preceding experiment, from 12 g of propargyl alcohol, 18 g of (C₂H₅)₃GeH, and 2–3 drops of catalyst, 16 g of (C₂H₅)₃GeCH=CHCH₂OH was obtained, b.p. 112–113° at 12 mm. Yield 37%.

Table 2

Raman spectrum, $\Delta \nu$ in cm$^{-1}$: 173(10), 293(3), 491(1), 526(4), 549(10 sh), 583(10 sh), 921(1), 979(5), 1024(4 sh), 1088(0), 1104(4), 1168(1), 1226(10), 1251(1), 1302(4), 1384(0), 1408(1), 1432(2), 1463(6), 1621(4), 2829(1), 2878(9), 2910(10), 2933(8), 2961(8).

γ-(Triethylgermyl)-propargyl alcohol $(\mathrm{C_2H_5})_3\mathrm{GeC}\equiv\mathrm{CCH_2OH}$. To $\mathrm{C_2H_5MgBr}$, prepared in 0.3 l of ether from 25 g of Mg and 120 g of ethyl bromide, 20 g of propargyl alcohol was added, and after 5 hr, 70 g of $(\mathrm{C_2H_5})_3\mathrm{GeBr}$. After boiling for 2 hr, the contents of the flask were decomposed with 10% HCl. After the usual workup, 15 g of $(\mathrm{C_2H_5})_4\mathrm{Ge}$ and 42 g of $(\mathrm{C_2H_5})_3\mathrm{GeC}\equiv\mathrm{CCH_2OH}$ were isolated, b.p. 111–2° at 9 mm. Yield 67%.

γ-(Trimethylgermyl)-propyl thioacetate $(\mathrm{CH_3})_3\mathrm{GeCH_2CH_2CH_2SOCCH_3}$. Addition of 20 g of thioacetic acid to 16 g of allyltrimethylgermane was accompanied by self-heating of the mixture. After heating this mixture for half an hour at 50°, vacuum distillation gave 22 g of $(\mathrm{CH_3})_3\mathrm{GeCH_2CH_2CH_2SOCCH_3}$, b.p. 90–91° at 7 mm. Yield 94%.

γ-Thiolpropyltrimethylgermane $(\mathrm{CH_3})_3\mathrm{GeCH_2CH_2CH_2SH}$. To a solution of 5 g of NaOH in 25 ml of water and 12 ml of alcohol, 18 g of γ-(trimethylgermyl)-propyl thioacetate was added. Vigorous stirring and boiling under a nitrogen atmosphere of the contents of the flask were continued for 3 hr. Then the organic layer was separated from the aqueous layer, and the latter was extracted with ether. After drying with $\mathrm{Na_2SO_4}$, vacuum distillation gave 10 g of $(\mathrm{CH_3})_3\mathrm{GeCH_2CH_2CH_2SH}$, b.p. 54–55° at 8 mm. Yield 68%.

β-(γ-(Trimethylgermyl)-propylmercapto)-propionitrile $(\mathrm{CH_3})_3\mathrm{GeCH_2CH_2CH_2SCH_2CH_2CN}$. To 9 g of γ-thiolpropyltrimethylgermane, 1–2 drops of a solution of sodium methylate in methyl alcohol were added, and then 5 g of acrylonitrile was added at such a rate that the temperature did not rise above ~70°. The liquid was then washed with dilute HCl, dried with $\mathrm{CaCl_2}$, and distilled. Obtained: 6 g of $(\mathrm{CH_3})_3\mathrm{Ge(CH_2)_3SCH_2CH_2CN}$, b.p. 144–46° at 8 mm. Yield 45%.

Zelinsky Institute of Organic Chemistry
Academy of Sciences of the USSR

Received
22 II 1961

REFERENCES CITED

1. A. D. Petrov, V. F. Mironov, N. G. Dzhurinskaya, DAN, 128, 302 (1959).
2. V. F. Mironov, N. G. Dzhurinskaya, A. D. Petrov, DAN, 131, 98 (1960).
3. E. G. Rochow, R. Didchenko, R. C. West, J. Am. Chem. Soc., 73, 5486 (1951).
4. H. H. Anderson, J. Am. Chem. Soc., 79, 326 (1957).
5. G. I. M. Vander Kerk, I. G. Noltes, I. G. A. Luijten, J. Appl. Chem., 7, No. 7, 366 (1957).
6. A. L. Allred, E. G. Rochow, J. Inorg. and Nucl. Chem., 5, 269 (1958).
7. V. F. Mironov, N. G. Maksimova, Izv. AN SSSR, OKhN, 1960, 2059.
8. V. F. Mironov, N. A. Pogonkina, Izv. AN SSSR, OKhN, 1960, 1998.
9. A. D. Petrov, S. I. Sadykh-Zade, DAN, 121, 119 (1958).
10. M. Lesbre, I. Satge, C. R., 247, No. 4, 471 (1958).