The reaction of diphenylphosphine oxide and diphenylphosphine with dialkyl azodicarboxylates

Abstract

Diphenylphosphine oxide reacts rapidly with azodicarboxylates to give 1 : 1 diphenyl-phosphinoylhydrazine-1,2-dicarboxylate adducts. Structural analysis shows that the diethyl compound crystallises in space group P, a= 12.197(5), b= 9.507(3), c= 8.503(6)Å, α= 85.83(5), β= 76.91 (6), γ= 75.61(3)° and the diisopropyl compound crystallises in space group P2₁/c, a= 21.344(6), b= 9.702(2), c= 10.929(4)Å, β= 104.71(3)°. The solid state conformations of the two molecules differ. In the diisopropyl structure the nitrogen protons and phosphorus oxygen atoms lie trans to each other whereas in the diethyl structure they are cis. ¹H and ¹³C NMR spectroscopic studies reveal a high degree of hindered rotation. The mechanism of the reaction is discussed. Unexpectedly, diphenylphosphine and diisopropyl azodicarboxylate react slowly to give a complex mixture of products.