Umsetzungen einiger β‐substituierter Acrylnitrile mit Diäthylphosphin. cis‐ und trans‐β‐Diäthylphosphino‐acrylnitril

Abstract

cc-und P-Chlor-, P-Benzylmercapto-und P-Tosyloxy-acrylnitril liefern mit Diathylphosphin cis-und trans-P-Diathylphosphino-acrylnitril, dessen Reaktionen untersucht werden. Aus Acrylnitril und Diathylchlorphosphin entsteht ein 1 : I-Additionsprodukt mit der vermutlichen Struktur eines Epiphosphoniumsalzes. *) Teil der Dissertat.

Synthesis and Coordination Chemistry of Cyano-Substituted Phosphines

“…However under basic catalytic conditions the reaction of diethyl phosphine with such olefins is noted to proceed partially as the substitution of the -functional group yielding the (E)-2-diethylphosphinoacrylonitrile in 45% yield (Scheme 21) [45].…”

“…Naturally, 2-diethylphosphinoacrylonitrile may be used as a substrate either in further hydrophosphination or in reaction with another nucleophile (Scheme 22) [45].…”

“…For example, reaction of dibutylphosphine with acrylonitrile giving Bu2PCH2CH2CN in 75% yield requires cooling at the addition step to 5-10 °C [44]. Addition of diethylphosphine to substituted acrylonitrile derivatives proceeds even at -20 °C (Scheme 21) [45].…”

“…As the rate of hydrophosphination is determined by the basicity of a phosphine, dialkylphosphines accordingly are more reactive [44,45]. For example, reaction of dibutylphosphine with acrylonitrile giving Bu2PCH2CH2CN in 75% yield requires cooling at the addition step to 5-10 °C [44].…”