Summary
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1.
A study was made of the reaction of acetylene and of various monosubstituted acetylenes with lithium, sodium, and potassium aluminum hydrides, which leads to the formation of complex aluminum acetylides MA1(C ≡ CR)4. The general character of the reaction was shown.
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2.
The effect of solvents on the rate of this reaction was established, and its catalytic character was shown. Inhibitors for this reaction were found (RX, AlX3, R2AlH, R3Al).
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3.
In presence of a dialkylaluminum hydride the reaction between alkali metal aluminum hydrides and acetylenic compounds goes differently, depending on the solvent used. In a strongly solvating solvent the main course is the addition of the aluminum hydride at the triple bond with formation of complex alkenyl compounds.
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4.
The reaction of monosubstituted acetylenes with the complexes NaAlR(4-n)Hn was investigated. It was shown that steric factors affect the course of this reaction. In a hydrocarbon medium the reaction goes strictly selectively with formation of the mixed acetylides NaAlR(4-n)(C≡CR')n. In a solvating solvent metalation is accompanied to a greater or less degree, depending on the structure of the complex NaAlR(4_n)Hn, by addition at the triple bond. Small additions of a dialkylaluminum hydride suppress the metalation reaction.
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This article is published in accordance with a resolution of the Conference of Editors-in-Chief of the journals of the Academy of Sciences of the USSR of July 12, 1962, as a dissertation paper by L. L. Ivanov.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya No. 11, pp. 1989–1998, November, 1964
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Ivanov, L.L., Gavrilenko, V.V. & Zakharkin, L.I. Reactions of mono substituted acetylenes with lithium, sodium, and potassium aluminum hydrides and with their alkyl derivatives of type malr(4-n)Hn . Russ Chem Bull 13, 1893–1899 (1964). https://doi.org/10.1007/BF00844483
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DOI: https://doi.org/10.1007/BF00844483