Microwave-assisted synthesis of N,N-bis(phosphinoylmethyl)amines and N,N,N-tris(phosphinoylmethyl)amines bearing different substituents on the phosphorus atoms

Abstract

A family of N,N-bis(phosphinoylmethyl)amines bearing different substituents on the phosphorus atoms was synthesized by the microwave-assisted and catalyst-free Kabachnik–Fields reaction of (aminomethyl)phosphine oxides with paraformaldehyde and diphenylphosphine oxide. The three-component condensation of N,N-bis(phosphinoylmethyl)amine, paraformaldehyde and a secondary phosphine oxide affording N,N,N-tris(phosphinoylmethyl)amine derivatives was also elaborated. This method is a novel approach for the synthesis of the target products.

New N-acyl- as well as N-phosphonoylmethyl- and N-phosphinoylmethyl-α-amino-benzylphosphonates by acylation and a tandem Kabachnik–Fields protocol

“…Earlier symmetric and asymmetric tris(phosphinoylmethyl)-amines were prepared by us by reacting the corresponding bis derivatives further with formaldehyde and secondary phosphine oxides. 54…”

“…Earlier symmetric and asymmetric tris( phosphinoylmethyl)-amines were prepared by us by reacting the corres-ponding bis derivatives further with formaldehyde and secondary phosphine oxides. 54 A total of 9 new derivatives were synthesized by N-acylation, or another phospha-Mannich step starting from simple α-aminophosphonates. In addition, 3 additional derivatives mentioned in the literature were fully characterized.…”

“…27,28,30 A special approach is the so-called bis Kabachnik-Fields protocol, in which the primary amine is reacted with two equivalents of the aldehyde (mostly formaldehyde) and with a similar amount of dialkyl phosphite or secondary phosphine oxide to furnish bis( phosphonoylmethyl)-or bis( phosphinoylmethyl)amines, respectively. [31][32][33][34][35][36] In a special procedure, treatment of aromatic aldehydes with ammonia, followed by reaction with diethyl phosphite in the presence of acetyl chloride as the catalyst furnished the corresponding bis( phosphonoylbenzyl)amines. 37 A few other methods were also described for the preparation of bis derivatives.…”

Synthesis of α-Aminophosphonates and Related Derivatives; The Last Decade of the Kabachnik–Fields Reaction

“…A series of amines was utilized in a tandem Kabachnik–Fields reaction to afford the corresponding nonsymmetric bis(phosphinoylmethyl)amines ( 79 ) after a two-step transformation ( Scheme 53 (1)). Subsequently, after debenzylation of intermediate 79 (R = Bn) to species 80 (the details were not reported), valuable tris derivatives ( 81 ) were prepared ( Scheme 53 (2)) [ 79 ].…”

An Overview of Microwave‐Assisted Kabachnik‐Fields Reactions

“…Conversely, green and facile approach has been adopted by Balint et al for acquiring hydroxylsubstituted α-aminophosphonates and α-aminohosphine oxide. 49 The sequential condensation of ethanolamine, paraformaldehyde and diethylphosphite was achieved in 54 % in a solvent and catalyst-free system, when exposed to MW radiations at 80°C for 20 min (Scheme 46). The scope of the reaction was further evaluated with secondary aminoalcohols which proceeded under the same conditions to produce much pro-nounced conversion of 95 % (Scheme 47).…”