49802-22-4

Upstream product

• 95220-16-9 Diphenyl-N-chlor-N-phenylphosphoramidat 
• 3848-51-9 phenyl-amidophosphoric acid diphenyl ester 
• 106-47-8 4-chloro-aniline 
• 2524-64-3 chlorophosphoric acid diphenyl ester 
• 4712-55-4 diphenyl hydrogen phosphite 
• 6971-73-9 N-p-chlorophenylphosphoramidic dichloride 
• 108-95-2 phenol 

Relevant academic research and scientific papers

Kinetics and mechanism of the anilinolysis of bis(aryl) chlorophosphates in acetonitrile

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.

Kinetics and mechanism of the aminolysis of phenyl substituted phenyl chlorophosphates with anilines in acetonitrile

The kinetics and mechanism of the aminolysis of phenyl substituted phenyl chlorophosphates with anilines are investigated in acetonitrile at 55.0°C. Very sensitive variation of ρY (δρY ? 0) with the change of substituent on the nucleophile (δσX) leads to a large negative cross-interaction constant, ρXY = (δρY)/(δσX) = -1.31. The secondary kinetic isotope effects observed with deuterated aniline nucleophiles are of the inverse type (kH/kD = 0.61-0.87), and small ΔH? (1.6-9.7 kcal mol-1) and large negative ΔS? (-43 to -65 e.u.) values are obtained. These results are consistent with a concerted process with a late, product-like transition state in which both bond making and leaving group departure are extensive.

Nucleophilic Substitution at the Tetracoordinated Phosphorus Atom. Reactivity of Amines towards Diphenyl Chlorophosphate in Acetonitrile

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