Abstract Generated abstract
This study examines the addition of triethylgermane to several tertiary vinyl ethynyl carbinols in the presence of Speier’s catalyst and the subsequent dehydration of the resulting diene germanium-containing carbinols. Dimethyl, methylethyl, tetramethylene, and pentamethylene substrates were converted to triethylgermyl diene carbinols under mild conditions, with products characterized by boiling point, refractive index, density, molar refraction, and elemental and hydroxyl analyses. Compared with analogous triethylsilane reactions, the triethylgermane reactions proceeded more smoothly, required less catalyst, and gave higher yields, generally about 69 to 79 percent. Dehydration with potassium bisulfate afforded the corresponding germanium-containing trienes in good yield for acyclic cases, while cyclopentyl and cyclohexyl derivatives showed partial decomposition during distillation and lower isolated yields.
Full Text
Chemistry
I. M. Gverdtsiteli, T. P. Guntsadze,
Corresponding Member of the Academy of Sciences of the USSR A. D. Petrov
Synthesis and Dehydration of Some Diene Germanium-Containing Carbinols
In previous works \((^1,\ ^2)\) we studied the action of \((\mathrm{C_2H_5})_3\mathrm{SiH}\) on vinylacetylenic carbinols in the presence of Pt/C catalysts and a 0.1 \(M\) solution of \(\mathrm{H_2PtCl_6}\) in isopropyl alcohol. It was found that with Speier’s catalyst the reaction proceeded under milder conditions than with the Pt/C catalyst: at room temperature, with better yields, and faster. It was of interest to study the behavior of \((\mathrm{C_2H_5})_3\mathrm{GeH}\) \((^3)\) in reaction with vinyl ethynyl carbinols under the same conditions (Speier’s catalyst).
For this purpose we carried out the synthesis of several tertiary carbinols, namely dimethyl-, methylethyl-, tetramethylene-, and pentamethylene-divinylgermanium carbinols (in the presence of Speier’s catalyst), and their dehydration.
As a result of the investigations it was found that the reaction between \((\mathrm{C_2H_5})_3\mathrm{GeH}\) and the above-mentioned carbinols proceeds more smoothly than in the case of \((\mathrm{C_2H_5})_3\mathrm{SiH}\): in each synthesis two fractions were isolated (whereas in the case of \((\mathrm{C_2H_5})_3\mathrm{SiH}\) several fractions were obtained), less catalyst was required (1 ml instead of 2 ml), and the yields increased to 70–80% (instead of 55–60%).
The reaction proceeded according to the scheme:
\[ \begin{gathered} \mathrm{R{-}C{-}C{\equiv}C{-}CH{=}CH_2} \;+\; (\mathrm{C_2H_5})_3\mathrm{GeH} \;\longrightarrow\; \mathrm{R{-}C{-}C{=}CH{-}CH{=}CH_2} \\[-2mm] \phantom{\mathrm{R{-}}}\big| \qquad\qquad\qquad\qquad\qquad \phantom{\mathrm{R{-}C{-}}}\big|\ \big| \\ \phantom{\mathrm{R{-}}}\mathrm{OH} \qquad\qquad\qquad\qquad\qquad \phantom{\mathrm{R{-}C{-}}}\mathrm{OH}\ \mathrm{Ge(C_2H_5)_3} \end{gathered} \]
where
\[ \mathrm{R} = \begin{matrix} \mathrm{CH_3}\\[-1mm] \mathrm{CH_3} \end{matrix} \!\!>\ ; \qquad \begin{matrix} \mathrm{C_2H_5}\\[-1mm] \mathrm{CH_3} \end{matrix} \!\!>\ ; \qquad \mathrm{C_5H_8}^{*}; \qquad \mathrm{C_6H_{10}}^{**}; \]
Dehydration of the diene compounds in the presence of \(\mathrm{KHSO_4}\) proceeded with good yields (74–82%); however, in the case of cyclopentyl and cyclohexyl radicals, partial decomposition was observed during distillation and, accordingly, the yield of the dehydrated product decreased (33–50%).
The properties and formulas of the compounds synthesized by us are given in Table 1.
Experimental Part
Action of \((\mathrm{C_2H_5})_3\mathrm{GeH}\) on dimethylvinylethynylcarbinol.
15 g of dimethylvinylethynylcarbinol, 1 ml of a 0.1 \(M\) solution of \(\mathrm{H_2PtCl_6}\) in isopropyl alcohol, and 23 g of \((\mathrm{C_2H_5})_3\mathrm{GeH}\) were placed in a three-necked flask with a stir—
\[ {}^{*}\quad \begin{gathered} \mathrm{CH_2{-}CH_2}\\[-1mm] \big| \qquad \backslash\\[-1mm] \mathrm{CH_2{-}CH_2}\!>\mathrm{C{-}C{=}CH{-}CH{=}CH_2}\\[-1mm] \phantom{\mathrm{CH_2{-}CH_2}}\big|\ \big|\\[-1mm] \phantom{\mathrm{CH_2{-}CH_2}}\mathrm{OH}\ \mathrm{Ge(C_2H_5)_3} \end{gathered} \]
\[ {}^{**}\quad \begin{gathered} \mathrm{CH_2{-}CH_2}\\[-1mm] / \qquad\quad \backslash\\[-1mm] \mathrm{CH_2}\qquad\ \mathrm{C{-}C{=}CH{-}CH{=}CH_2}\\[-1mm] \backslash \qquad\quad / \quad \big|\ \big|\\[-1mm] \mathrm{CH_2{-}CH_2}\qquad \mathrm{OH}\ \mathrm{Ge(C_2H_5)_3} \end{gathered} \]
Table 1
| No. | Compound obtained | B.p., °C (mm Hg) | \(n_D^{20}\) | \(d_4^{20}\) | \(MR_D\), found | \(MR_D\), calculated | Yield, % | Found, % C | Found, % H | Found, % Ge | Calculated, % C | Calculated, % H | Calculated, % Ge | OH, % found | OH, % calculated |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1 | \(\begin{array}{c}\mathrm{CH_3}\\[-2pt]\mathrm{CH_3}\end{array}\!\!\begin{array}{c}\diagdown\\[-2pt]\diagup\end{array}\!\mathrm{C{-}C{=}CH{-}CH{=}CH_2}\) \(\qquad\quad \mathrm{\vert}\ \ \mathrm{\vert}\) \(\qquad\quad \mathrm{OH}\ \mathrm{Ge(C_2H_5)_3}\) |
112 (6) | 1,4954 | 1,0390 | 76,02 | 74,64 | 70 | 57,54 | 9,59 | 26,50 | 57,64 | 9,60 | 26,82 | 7,50 | 7,32 |
| 2 | \(\mathrm{CH_2{=}C{-}C{=}CH{-}CH{=}CH_2}\) \(\qquad\ \mathrm{\vert}\ \ \mathrm{\vert}\) \(\qquad\ \mathrm{CH_3}\ \mathrm{Ge(C_2H_5)_3}\) |
71 (2) | 1,5016 | 1,0216 | 72,92 | 72,62 | 82 | 61,10 61,29 |
9,57 9,56 |
28,26 28,32 |
61,90 | 9,50 | 28,74 | — | — |
| 3 | \(\begin{array}{c}\mathrm{C_2H_5}\\[-2pt]\mathrm{CH_3}\end{array}\!\!\begin{array}{c}\diagdown\\[-2pt]\diagup\end{array}\!\mathrm{C{-}C{=}CH{-}CH{=}CH_2}\) \(\qquad\quad \mathrm{\vert}\ \ \mathrm{\vert}\) \(\qquad\quad \mathrm{OH}\ \mathrm{Ge(C_2H_5)_3}\) |
98—100 (3) | 1,4972 | 1,0430 | 79,61 | 78,27 | 79 | 52,64 52,09 |
10,04 10,01 |
25,69 25,40 |
51,98 | 9,83 | 25,50 | 7,47 7,31 |
6,40 |
| 4 | \(\begin{array}{c}\mathrm{CH_3CH}\\[-2pt]\mathrm{CH_3}\end{array}\!\!\begin{array}{c}\diagdown\\[-2pt]\diagup\end{array}\!\mathrm{C{-}C{=}CH{-}CH{=}CH_2}\) \(\qquad\qquad\ \mathrm{\vert}\) \(\qquad\qquad\ \mathrm{Ge(C_2H_5)_3}\) |
107—108 (3) | 1,4965 | 1,0367 | 75,52 | 77,35 | 74 | 62,57 62,65 |
9,99 10,03 |
27,21 27,19 |
62,98 | 6,75 | 27,22 | — | — |
| 5 | \(\mathrm{C_4H_9C(OH)C{\equiv}CH{-}CH{=}CH_2}\) \(\qquad\qquad \mathrm{\vert}\) \(\qquad\qquad \mathrm{Ge(C_2H_5)_3}\) |
116—118 (1) | 1,5120 | 1,0788 | 82,49 | 81,74 | 73 | 60,32 60,40 |
10,01 9,97 |
24,99 24,97 |
60,69 | 9,44 | 24,47 | 6,30 | 5,75 |
| 6 | \(\mathrm{C_4H_7{=}C{-}C{=}CH{-}CH{=}CH_2}\) \(\qquad\qquad \mathrm{\vert}\) \(\qquad\qquad \mathrm{Ge(C_2H_5)_3}\) |
120—122 (3) | 1,5160 | 1,0530 | 78,67 | 79,80 | 33 | 64,52 | 9,66 | 25,93 | 64,60 | 9,33 | 26,06 | ||
| 7 | \(\mathrm{C_2H_{10}C(OH)C{\equiv}CH{-}CH{=}CH_2}\) \(\qquad\qquad \mathrm{\vert}\) \(\qquad\qquad \mathrm{Ge(C_2H_5)_3}\) |
114—116 (1) | 1,5140 | 1,0777 | 86,93 | 86,42 | 69 | 60,82 60,89 |
9,80 9,75 |
23,46 23,40 |
61,81 | 9,65 | 23,73 | 6,21 5,97 |
5,46 |
| 8 | \(\mathrm{C_5H_9{=}C{-}C{\equiv}CH{-}CH{=}CH_2}\) \(\qquad\quad \mathrm{\vert}\) \(\qquad\quad \mathrm{Ge(C_2H_5)_3}\) |
139—140 (4) | 1,5180 | 1,0332 | 85,80 | 84,42 | 50 | 65,81 65,90 |
9,84 9,80 |
24,84 24,73 |
65,62 | 9,57 | 24,81 | — | — |
mechanical stirrer. After 5 min a vigorous reaction began (the contents of the flask boiled). After approximately an hour the reaction was complete.
By vacuum distillation under nitrogen the following fractions were isolated: I, 93–110° (6 mm), 2.5 g; II, 112° (6 mm), in an amount of 30 g (yield 70%). For fraction II, \(n_D^{20} 1.4954\), \(d_4^{20} 1.0390\) were found. The substance obtained—2-methyl-3-triethylgermylhexadien-3,5-ol-2—is a yellowish viscous liquid, for which \(MR_D\) was calculated as 74.64, found 76.02.
\[ \begin{aligned} &\text{Found, \%: } &&\mathrm{C}\ 57.54;\ \mathrm{H}\ 9.59;\ \mathrm{Ge}\ 26.58;\ (\mathrm{OH})\ 7.39,\ 7.50 \\ &\mathrm{C}_{13}\mathrm{H}_{26}\mathrm{GeO}.\ \text{Calculated, \%: } &&\mathrm{C}\ 57.64;\ \mathrm{H}\ 9.60;\ \mathrm{Ge}\ 26.82;\ (\mathrm{OH})\ 7.32 \end{aligned} \]
Dehydration of 2-methyl-3-triethylgermylhexadien-3,5-ol-2. 5 g of the substance to be dehydrated, 2.5 g of \( \mathrm{KHSO_4} \), and 0.1 g of dithizone (antioxidant) were heated in vacuum under nitrogen for 20 min (90–100°), after which distillation was carried out; 3.7 g of 2-methyl-3-triethylgermylhexatriene-1,3,5 was obtained, b.p. 71° (2 mm), \(n_D^{20} 1.5016\), \(d_4^{20} 1.0216\), a mobile yellow liquid, yield 82%. \(MR_D\) calculated 72.62, found 72.92.
\[ \begin{aligned} &\text{Found, \%: } &&\mathrm{C}\ 61.20,\ 61.10;\ \mathrm{H}\ 9.57,\ 9.56;\ \mathrm{Ge}\ 28.26,\ 28.32 \\ &\mathrm{C}_{13}\mathrm{H}_{24}\mathrm{Ge}.\ \text{Calculated, \%: } &&\mathrm{C}\ 61.90;\ \mathrm{H}\ 9.50;\ \mathrm{Ge}\ 28.74 \end{aligned} \]
Hydroxyl was not detected.
Action of \((\mathrm{C}_2\mathrm{H}_5)_3\mathrm{GeH}\) on methylethylvinylethynylcarbinol. 18.8 g (0.15 mole) of the starting carbinol, 1 ml of Speier’s catalyst, and 24 g (0.15 mole) of \((\mathrm{C}_2\mathrm{H}_5)_3\mathrm{GeH}\) were taken. The reaction proceeded analogously to that described previously.
By vacuum distillation under nitrogen the following fractions were isolated: I, 46–98° (3 mm), 4.5 g; II, 98–100° (3 mm), 33.1 g, yield 79%; for fraction II, \(n_D^{20} 1.4972\), \(d_4^{20} 1.0430\).
The substance obtained, 3-methyl-4-triethylgermylheptadien-4,6-ol-3, is a yellowish liquid, for which \(MR_D\) was calculated as 78.27, found 79.61.
\[ \begin{aligned} &\text{Found, \%: } &&\mathrm{C}\ 52.64,\ 52.09;\ \mathrm{H}\ 10.04,\ 10.01;\ \mathrm{Ge}\ 25.69,\ 25.40;\ (\mathrm{OH})\ 7.47,\ 7.31 \\ &\mathrm{C}_{14}\mathrm{H}_{28}\mathrm{GeO}.\ \text{Calculated, \%: } &&\mathrm{C}\ 51.98;\ \mathrm{H}\ 9.83;\ \mathrm{Ge}\ 25.50;\ (\mathrm{OH})\ 6.40 \end{aligned} \]
Dehydration of 3-methyl-4-triethylgermylheptadien-4,6-ol-3. 4.26 g (0.015 mole) of the substance, 2.5 g of calcined \( \mathrm{KHSO_4} \), and 0.1 g of dithizone were taken. The reaction was carried out analogously to that described previously.
The substance obtained, 3-methyl-4-triethylgermylheptatriene-1,3,5, b.p. 107–108° (3 mm), is a yellow mobile liquid, \(n_D^{20} 1.4965\), \(d_4^{20} 1.0367\). Yield 74% (2.9 g). \(MR_D\) calculated 77.35, found 75.52.
\[ \begin{aligned} &\text{Found, \%: } &&\mathrm{C}\ 62.65,\ 62.57;\ \mathrm{H}\ 9.99,\ 10.03;\ \mathrm{Ge}\ 27.21,\ 27.19 \\ &\mathrm{C}_{14}\mathrm{H}_{26}\mathrm{Ge}.\ \text{Calculated, \%: } &&\mathrm{C}\ 62.98;\ \mathrm{H}\ 9.57;\ \mathrm{Ge}\ 27.22 \end{aligned} \]
Hydroxyl was not detected.
Action of \((\mathrm{C}_2\mathrm{H}_5)_3\mathrm{GeH}\) on tetramethylenevinylethynylcarbinol. 20 g of the starting carbinol (0.15 mole), 28 g of \((\mathrm{C}_2\mathrm{H}_5)_3\mathrm{GeH}\), and 1 ml of Speier’s catalyst were taken. The reaction proceeded analogously to the preceding ones. By vacuum distillation under nitrogen the following were obtained: fraction I, 70–116°, 3.3 g; fraction II, 116–118° (1 mm), 32 g of substance. For fraction II, \(n_D^{20} 1.5120\), \(d_4^{20} 1.0788\), yield 73% of theoretical.
The substance obtained, 1-oxocyclopentyl-1-triethylgermylbutadiene-1,3, is a viscous pale-yellow liquid, for which \(MR_D\) was calculated as 81.742, found 82.497.
\[ \begin{aligned} &\text{Found, \%: } &&\mathrm{C}\ 60.32,\ 60.40;\ \mathrm{H}\ 10.01,\ 9.97;\ \mathrm{Ge}\ 24.99,\ 24.97;\ (\mathrm{OH})\ 6.49,\ 6.30 \\ &\mathrm{C}_{15}\mathrm{H}_{28}\mathrm{GeO}.\ \text{Calculated, \%: } &&\mathrm{C}\ 60.62;\ \mathrm{H}\ 9.44;\ \mathrm{Ge}\ 24.47;\ (\mathrm{OH})\ 5.75 \end{aligned} \]
Dehydration of 1-oxycyclopentyl-1-triethylgermylbutadiene-1,3. 3 g of the substance to be dehydrated, 2 g of KHSO₄, and 0.1 g of dithizone were taken. The reaction was carried out analogously to that described earlier.
By distillation in vacuo under nitrogen, a substance was obtained with b.p. 120–122° (3 mm), \(n_D^{20}\) 1.5160, \(d_4^{20}\) 1.0530. During the distillation, decomposition was observed, as a result of which the yield of the dehydrated product decreased considerably—to 33% (0.9 g).
The substance obtained, 1-cyclopenten-1,1-triethylgermylbutadiene-1,3, is a yellow mobile liquid, for which \(MR_D\) was found to be 78.67, calculated 79.806.
\[ \begin{aligned} &\text{Found, \%: } &&\mathrm{C}\ 64.42,\ 64.52;\quad \mathrm{H}\ 9.65,\ 9.66;\quad \mathrm{Ge}\ 25.42,\ 25.98\\ &\mathrm{C}_{15}\mathrm{H}_{26}\mathrm{Ge}.\ \text{Calculated, \%: } &&\mathrm{C}\ 64.60;\quad \mathrm{H}\ 9.33;\quad \mathrm{Ge}\ 26.06 \end{aligned} \]
Hydroxyl was not detected.
Action of \((\mathrm{C}_2\mathrm{H}_5)_3\mathrm{GeH}\) on pentamethylenevinylethynylcarbinol. 23 g (0.15 mole) of carbinol, 1 ml of Speier catalyst, and 25 g (0.15 mole) of \((\mathrm{C}_2\mathrm{H}_5)_3\mathrm{GeH}\) were taken. The reaction proceeded analogously to the preceding one.
After distillation in vacuo under nitrogen, the following were obtained: fraction I up to 114° (1 mm), 4 g; fraction II, 144–116° (1 mm), 28 g. For fraction II, \(n_D^{20}\) 1.5140, \(d_4^{20}\) 1.0777 were found. Yield 69%.
The substance obtained, oxycyclohexyl-1-triethylgermylbutadiene-1,3, is a viscous pale-yellow liquid, for which \(MR_D\) was calculated as 86.42, found 86.93.
\[ \begin{aligned} &\text{Found, \%: } &&\mathrm{C}\ 60.82,\ 60.89;\quad \mathrm{H}\ 9.80,\ 9.75;\quad \mathrm{Ge}\ 23.46,\ 23.40;\quad (\mathrm{OH})\ 6.21;\ 5.97\\ &\mathrm{C}_{16}\mathrm{H}_{30}\mathrm{GeO}.\ \text{Calculated, \%: } &&\mathrm{C}\ 61.81;\quad \mathrm{H}\ 9.65;\quad \mathrm{Ge}\ 23.73;\quad (\mathrm{OH})\ 6.46 \end{aligned} \]
Dehydration of 1-oxycyclohexyl-1-triethylgermylbutadiene-1,3. 3.1 g (0.1 mole) of the substance to be dehydrated, 2 g of KHSO₄, and 0.1 g of dithizone were taken. The reaction was carried out analogously to the preceding one.
During distillation, as in the case of the cyclopentyl radical, partial decomposition was observed; as a result, 1.5 g of substance was obtained with b.p. 139–140° (4 mm), \(n_D^{20}\) 1.5180, \(d_4^{20}\) 1.0332. Yield 50%. The substance obtained, 1-cyclohexen-1-1-triethylgermylbutadiene-1,3, is a yellow mobile liquid, for which \(MR_D\) was calculated as 84.424, found 85.80.
\[ \begin{aligned} &\text{Found, \%: } &&\mathrm{C}\ 65.81,\ 65.90;\quad \mathrm{H}\ 9.84,\ 9.80;\quad \mathrm{Ge}\ 24.84,\ 24.73\\ &\mathrm{C}_{16}\mathrm{H}_{28}\mathrm{Ge}.\ \text{Calculated, \%: } &&\mathrm{C}\ 65.62;\quad \mathrm{H}\ 9.57;\quad \mathrm{Ge}\ 24.81 \end{aligned} \]
Hydroxyl was not detected.
Tbilisi
State University
Received
26 VI 1963
CITED LITERATURE
- A. D. Petrov, I. M. Gverdtsiteli, K. I. Cherkezishvili, Tr. Tbil. gos. univ., 74, 121 (1959).
- A. D. Petrov, I. M. Gverdtsiteli, K. I. Cherkezishvili, DAN, 129, No. 4 (1959).
- H. N. Anderson, J. Am. Chem. Soc., 79, 326 (1957).