24625-67-0Relevant academic research and scientific papers
Practical Synthesis of Phosphinic Amides/Phosphoramidates through Catalytic Oxidative Coupling of Amines and P(O)?H Compounds
Tan, Chen,Liu, Xinyuan,Jia, Huanxin,Zhao, Xiaowen,Chen, Jian,Wang, Zhiyong,Tan, Jiajing
supporting information, p. 881 - 887 (2020/01/02)
Herein, we report a highly efficient ZnI2-triggered oxidative cross-coupling reaction of P(O)?H compounds and amines. This operationally simple protocol provides unprecedented generic access to phosphinic amides/phosphoramidate derivatives in good yields and short reaction time. Besides, the reaction proceeds under mild conditions, which avoids the use of hazardous reagents, and is applicable to scale-up syntheses as well as late-stage functionalization of drug molecules. The stereospecific coupling is also achieved from readily available optically enriched P(O)?H compounds.
Synthesis of nonsymmetrical dialkylamines on the basis of diphenylphosphinic amides
Bondarenko,Kharlamov,Vendilo
experimental part, p. 1872 - 1885 (2011/01/06)
A facile method for the synthesis of nonsymmetrical dialkylamines (C nH2n+1)2NH (n = 1-12) using the Ph 2P(O) protecting group was developed. The method includes successive transformation of monoalkylamines to primary diphenylphosphinic N-alkylamides Ph2P(O)NHR' (R' = CnH2n+1, n = 1-12) by the Todd-Atherton reaction, phase transfer N-alkylation of these compounds, and hydrolysis of the secondary amides Ph2P(O)NR'R″ thus formed. When the (EtO)2P(O) and Bu2P(O) protecting groups are used, N-alkylation of primary amides is accompanied by the formation of Et-O and P-N bond cleavage products, respectively. A study of the stability of the N-alkylamides R2P(O)NHR' (R = Ph, p-MeC6H4, p-CIC6H4, Bu) under strong alkaline conditions used in the phase transfer N-alkylation showed that an increase in the electron-donating ability of substituents at both the nitrogen atom and the phosphorus atom results in a decrease in the degree of P-N bond cleavage. The primary and secondary diphenylphosphinic amides containing a β-hydroxyethyl group at the nitrogen atom are extremely unstable under the alkaline conditions and are converted quantitatively to the diphenylphosphinic acid salt.
Direct conversion of secondary phosphine oxides and h-phosphinates with [Di(acyloxy)iodo]benzenes to phosphinic and phosphonic amides
Hubacz, Anna,Makowiec, Slawomir
experimental part, p. 81 - 86 (2009/09/25)
The reaction of [di(acyloxy)iodo]- benzene with secondary phosphine oxides or H-phosphinates in the presence of primary or secondary amines allows one to obtain phosphinic or phosphonic acids amides in the one-pot process. We take advantage of the strong acylating system DAIB/R2P(O)H to phosphinylation of amines. However, the reaction mechanism is multipathway and causes yields of phosphinic or phosphonic acids amides to be moderate. When the concentration of amines is low, the intermolecular process plays a main role leading to the formation of carboxylic amides through mixed phosphoric-carboxylic anhydride, and also in the low concentration of amines, tetrahydrofuran effectively competes with the amines in the nucleophilic attack on the acylating intermediates.
THE AMINOLYSIS OF PHOSPHINATES; THE KINETICS AND MECHANISM OF THE AMINOLYSIS OF PHOSPHINATE ESTERS IN ACETONITRILE
Cook, Robert D.,Daouk, Wafa A.,Hajj, Asaad N.,Kabbani, Ahmad,Kurku, Anwar,et al.
, p. 213 - 219 (2007/10/02)
The aminolysis of aryl diphenylphosphinates, p-nitrophenyl diphenylphosphinothionate, -phosphinothioate, and -phosphinodithioate by n-butylamine, by the secondary amines piperidine, pyrrolidine, morpholine, and dipropylamine, as well as by a series of diamines, has been studied in acetonitrile.The general reactivity order is diamines > butylamine > sec-amines.Butylaminolysis follows a two-term rate law, one first order in amine and the other second order in amine.The second order in amine term predominates. sec-Amines and diamines follow a rate law which is first order in amine only.Leaving group effects, solvent effects, and activation parameters support a pathway which involves rate-determining collapse of a zwitterionic pentacoordinate intermediate.In the case of butylamine this collapse is general base catalyzed and for the diamines the reaction is intramolecularly general base catalyzed.
