62569-07-7

Upstream product

• 2101-86-2 p-methylazidobenzene 
• 4712-55-4 diphenyl hydrogen phosphite 
• 106-49-0 p-toluidine 
• 2524-64-3 chlorophosphoric acid diphenyl ester 
• 33862-27-0 N-(4-methylphenyl) phosphoramidic dichloride 
• 108-95-2 phenol 

Downstream Products

• 17739-97-8 4-methyl-2-[(4-methylphenyl)azo]-phenol 
• 94255-97-7 Diphenyl-N-chlor-N-p-tolyl-phosphoramidat 

Relevant academic research and scientific papers

The Step-Wise Synthesis of Oligomeric Phosphoramidates

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.

Redox-Neutral P(O)-N Coupling between P(O)-H Compounds and Azides via Dual Copper and Photoredox Catalysis

We report a redox-neutral P(O)-N coupling reaction of P(O)-H compounds with azides via photoredox and copper catalysis, providing new access to useful phosphinamides, phosphonamides, and phosphoramides. This transformation tolerates a wide range of nucleophilic functionalities including alcohol and amine nucleophiles, which makes up for the deficiency of classical nitrogen nucleophilic substitution reactions. As a demonstration of the broad potential applications of this new methodology, late-stage functionalization of a diverse array of azido-bearing natural products and drug molecules, a preliminary asymmetric reaction, and a continuous visible-light photoflow process have been developed.

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