Convenient synthesis of phosphonohydrazines from arylamines

Abstract

Phosphonohydrazines were prepared in good yield from corresponding arylamines by a one-pot reaction through diazotization with an organic nitrite and treatment with a trialkyl phosphite. The trialkyl phosphite is postulated to function as a nucleophile as well as a reducing agent.

Recent Development of Aryl Diazonium Chemistry for the Derivatization of Aromatic Compounds

“…As for the case of heteroatom nucleophiles, Slootweg and co-workers reported the facile synthesis of tunable aryl azophosphonium salts through the reaction of para -substituted aryl diazonium salts with tri tert -butylphosphine, leading to a range of colored compounds (16 examples, 55–96% yields) . Additionally, the one-pot reaction from anilines through diazotization and treatment with a trialkyl phosphite was reported, affording phosphonohydrazines in moderate yields (6 examples, 27–84% yields) . These two reactions utilized phosphine compounds as the nucleophiles.…”

“…423 Additionally, the one-pot reaction from anilines through diazotization and treatment with a trialkyl phosphite was reported, affording phosphonohydrazines in moderate yields (6 examples, 27−84% yields). 424 These two reactions utilized phosphine compounds as the nucleophiles. The construction of functionalized tetrazoles can be achieved through this trapping process with nitrogen nucleophiles.…”

Blue LED-Mediated Syntheses of Arylazo Phosphine Oxides and Phosphonates via N–P Bond Formation

“…Since then, not much has been published in this area, and only a few protocols have been developed for the preparation of arylazo phosphonates (Scheme 2). After almost 15 years, Wu and co-workers 11 in 2016 developed a synthetic pathway for the phosphinohydrazines via diazotization of arylamines with triisopropyl phosphines in the presence of isoamyl nitrite (Scheme 2a). However, in these strategies, the substrate scope was not studied thoroughly and was limited to only a few molecules.…”

Oxidation–Reduction Condensation of Diazaphosphites for Carbon–Heteroatom Bond Formation Based on Mitsunobu Mechanism

“…With the proposed reaction conditions, we hypothesized that the highly nucleophilic phosphinite A with azo compound B would generate a strongly basic hydrazo anion intermediate that can deprotonate nonacidic nucleophiles C . The resulting anionic nucleophile undergoes a substitution reaction with alkoxyphosphonium intermediates to afford alkylated amines D and phosphonohydrazines E as the sole byproducts, which also have been utilized as potential candidates for novel insecticides and for the synthesis of pharmaceutical compounds containing a P­(O)–N bond . This synthetic transformation would avoid the phosphine oxide and hydrazine byproduct formation common in the traditional Mitsunobu reaction.…”