76908-68-4Relevant academic research and scientific papers
A PARTICULARLY CONVENIENT ONE-POT SYNTHESIS OF N-ALKOXYCARBONYL, N-ACYL AND N-AROYL SUBSTITUTED IMINOPHOSPHORANES; IMPROVED PREPARATION OF AZIDOFORMATES, AROYL AND ALKANOYL AZIDES; AN ALTERNATIVE ROUTE TO COMPLEX AMIDES
Froeyen, Paul
, p. 161 - 172 (2007/10/02)
Chloroformates and acid chlorides react smoothly with sodium azide in acetone at 0 deg C, forming azidoformates, aroyl and alkanoyl azides in very high yield.With triphenylphosphine or other phosphines present in the reaction mixture, the forming azides are intercepted, leading directly to the corresponding N-alkanoyl, N-aroyl, N-alkoxycarbonyl, and N-aryloxycarbonyliminophosphoranes.N-acyliminophosphoranes react with n-butyllithium forming anions which react readily with electrophiles, e.g., carbonyl compounds, forming highly substituted iminophosphoranes.The phosphonium group is effortlessly removed from the latter compounds by acid hydrolysis forming the corresponding amides in high yield.Key words: Synthesis; iminophosphoranes; aroyl azides; alkanoyl azides; complex amides.
Synthesis of N-Acyl-, N-Sulfonyl-, and N-Phosphinylphospha-λ5-azenes by a Redox-Condensation Reaction Using Amides, Triphenylphosphine, and Diethyl Azodicarboxylate
Bittner, Shmuel,Assaf, Yonit,Krief, Penina,Pomerantz, Martin,Ziemnicka, Barbara T.,Smith, Christina G.
, p. 1712 - 1718 (2007/10/02)
The reaction of phosphines and amides with diethyl azodicarboxylate (DAD) produced phospha-λ5-azenes.Thus aromatic amides and those aliphathic amides with electron-withdrawing substituents gave N-acyl-P,P,P-triphenylphospha-λ5-azenes (5) when triphenylphosphine (TPP) was employed.Both aryl- and alkylsulfonamides reacted with TPP and DAD to produce the N-sulfonylphospha-λ5-azenes (9).Diphenylphosphinamide (10) and ethyl carbamate (12) also produced the respective phosphazenes (11 and 13) with TPP and DAD.Secondary carboxamides and sulfonamides did not react with TPP and DAD.The reaction of triethyl phosphite with sulfonamides in the presence of DAD produced the phosphorimidates (20) in an analogous reaction, along with the corresponding N,N-diethylsulfonamides and the deethylated adduct of triethyl phosphite and DAD (23).Triethyl phosphite-DAD failed, however, to give a phosphorimidate with carboxamides but gave, instead, the rearranged adduct of DAD and triethyl phosphite (19).Tris(dimethylamino)phosphine reacted with sulfonamides and DAD but the products were the corresponding ethyl N-sulfonylcarbamates (26) rather than the phosphazenes.Tris(dimethylamino)phosphine reacted with azodicarbonamide (a molecule which contains both the azo and carboxamide groups) with the production of N,N-dimethylurea, again without formation of the phosphazene.Finally, the reaction of triphenylarsine with benzenesulfonamide and DAD produced N-(phenylsulfonyl)triphenylarsa-λ5-azene (30) but triphenylstibene with DAD and benzenesulfonamide only gave triphenylstibene oxide.Mechanistic possibilities for these reactions are also discussed.
