62569-07-7Relevant articles and documents
The Step-Wise Synthesis of Oligomeric Phosphoramidates
Data, Shailja,Leung Wai, Jeffery,Kumar, Saawan,Cameron, Alan J.,Trehet, Manon,Itumoh, Emeka J.,Feld, Joey,S?hnel, Tilo,Leitao, Erin M.
supporting information, p. 5468 - 5477 (2021/09/30)
In this study, the step-wise synthesis to a series of higher phosphoramidates was explored, affording compounds containing N?P?N, symmetric and asymmetric P?N?P and P?N?P?N?P linkages. Salt elimination and lithiation strategies were employed to create the new P?N bonds. It was found that the steric bulk and electronic contribution of the substituents on the P(V) centers were important factors to the success of the reactions. The oligomeric phosphoramidates were characterized by multinuclear NMR and IR spectroscopies as well as ESI mass spectrometry. A selection of the synthesized P?N oligomers were evaluated for their antimicrobial activity against E.coli, S.aureus, C.albicans, and A.fumigatus at varying concentrations. The results suggest their potential use as environmentally friendly fire retardants as the minimal inhibitory concentration (MIC) value for all the compounds was found to be >128 μM, indicating that the compounds do not have any detectable antimicrobial activity.
Kinetics and mechanism of the anilinolysis of bis(aryl) chlorophosphates in acetonitrile
Barai, Hasi Rani,Lee, Hai Whang
scheme or table, p. 1939 - 1944 (2012/02/05)
The nucleophilic substitution reactions of bis(Y-aryl) chlorophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 35.0 °C. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorophosphates (2). The substrate 1 has one more identical substituent Y compared to substrate 2. The cross-interaction between Y and Y, due to additional substituent Y, is significant enough to result in the change of the sign of cross-interaction constant (CIC) from negative ρXY = -1.31 (2) to positive ρXY = +1.91 (1), indicating the change of reaction mechanism from a concerted SN2 (2) to a stepwise mechanism with a rate-limiting leaving group departure from the intermediate (1). The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines (XC6H4ND2) show secondary inverse, k H/kD = 0.61-0.87. The DKIEs invariably increase as substituent X changes from electron-donating to electron-withdrawing, while invariably decrease as substituent Y changes from electron-donating to electron-withdrawing. A stepwise mechanism with a rate-limiting bond breaking involving a predominant backside attack is proposed on the basis of positive sign of ρXY and secondary inverse DKIEs.
Nucleophilic Substitution at the Tetracoordinated Phosphorus Atom. Reactivity of Amines towards Diphenyl Chlorophosphate in Acetonitrile
Solomoichenko,Sadovskii,Savelova,Piskunova,Popov
, p. 1434 - 1441 (2007/10/03)
Tertiary alkylamines, pyridines, and imidazoles catalyze the hydrolysis of diphenylchlorophosphate (acetonitrile, 25°C) by a nucleophilic mechanism with the rate-determining attack of an amine on the substrate. Primary and secondary alkyl and arylamines f
