98579-83-0Relevant academic research and scientific papers
Synthesis of nonsymmetrical dialkylamines on the basis of diphenylphosphinic amides
Bondarenko,Kharlamov,Vendilo
, 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.
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.
