5449-04-7

Upstream product

• 85908-57-2 ethyl phenyl chlorophosphate 
• 62-53-3 aniline 
• 108-95-2 phenol 
• 1754-49-0 diethyl phenylphosphonate 
• 770-12-7 O-phenyl phosphorodichloridate 
• 139-02-6 sodium phenoxide 
• 142-04-1 aniline hydrochloride 
• 6955-57-3 phenylamidophosphoric dichloride 
• 51766-21-3 Phenyl N-phenylphosphoramidochloridate 

Relevant academic research and scientific papers

Evaluation and development of methodologies for the synthesis of thiophosphinic acids

Thiophosphorus acids R1R2P(S)OH constitute an important class of organophosphorus compounds, in which the phosphorus atom is intrinsically chiral if R1 ≠ R2. In connection with a project aimed at the preparation of chiral thiophosphorus acids, various available literature methods were considered, but few fit the requirement of odorless reagents. Herein, the results of our studies on the synthesis of thiophosphinic acids are reported. Ultimately, two major approaches were selected: (1) the Stec reaction of phosphorus amides with carbon disulfide; and (2) the one-pot synthesis of thiophosphorus acids from H-phosphinates, an organometallic nucleophile, and quenching with elemental sulfur. An application to the preparation of a potential chiral phosphorus organocatalyst is also reported.

Kinetics and mechanism of the anilinolysis of aryl ethyl isothiocyanophosphates in acetonitrile

The nucleophilic substitution reactions of Y-aryl ethyl isothiocyanophosphates with substituted X-anilines and deuterated X-anilines were investigated kinetically in acetonitrile at 75.0 oC. The free energy relationships with X in the nucleophiles exhibited biphasic concave downwards with a break point at X = H. A stepwise mechanism with rate-limiting bond formation for strongly basic anilines and with rate-limiting bond breaking for weakly basic anilines is proposed based on the negative and positive ?XY values, respectively. The deuterium kinetic isotope effects (DKIEs; kH/kD) changed gradually from primary normal with strongly basic anilines, via primary normal and secondary inverse with aniline, to secondary inverse with weakly basic anilines. The primary normal and secondary inverse DKIEs were rationalized by frontside attack involving hydrogen bonded, four-center-type TSf and backside attack involving in-line-type TSb, respectively.

Kinetics and mechanism of the anilinolysis of dibutyl chlorophosphate in acetonitrile

The nucleophilic substitution reactions of dibutyl chlorophosphate (3) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 55.0 °C. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse (kH/kD = 0.86-0.97) with the strongly basic anilines while primary normal (kH/kD = 1.04-1.10) with the weakly basic anilines. The DKIEs, steric effects of the two ligands, activation parameters, cross-interaction constants, variation trends of the kH/kD values with X, and mechanism are discussed for the anilinolyses of the nine (R1O)(R2O)P(=O)Cl-type chlorophosphates. A concerted mechanism is proposed with a backside nucleophilic attack transition state for the strongly basic anilines and with a frontside attack involving a hydrogen-bonded four-center-type transition state for the weakly basic anilines on the basis of the magnitudes, secondary inverse and primary normal, and variation trends of the kH/kD values with X.

Kinetics and mechanism of the anilinolysis of dibutyl chlorothiophosphate in acetonitrile

The nucleophilic substitution reactions of dibutyl chlorothiophosphate (4S) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 55.0 °C. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are primary normal (k H/kD = 1.10-1.35). A concerted mechanism involving predominant frontside nucleophilic attack is proposed on the basis of the primary normal DKIEs and selectivity parameters. Hydrogen bonded, four-center-type transition state is proposed. The steric effects of the two ligands on the anilinolysis rates of the chlorothiophosphates are discussed. The anilinolyses of P=S systems are compared with those of their P=O counterparts on the basis of the reactivities, thio effects, selectivity parameters, and DKIEs.

Kinetics and mechanism of anilinolysis of phenyl n-phenyl phosphoramidochloridate in acetonitrile

The kinetic studies on the reactions of phenyl N-phenyl phosphoramidochloridate (8) with substituted anilines (XC6H 4NH2) and deuterated anilines (XC6H 4ND2) have been carried out in acetonitrile at 60.0 oC. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are huge secondary inverse (kH/kD = 0.52-0.69). A concerted mechanism is proposed with a backside attack transition state (TS) on the basis of the secondary inverse DKIEs and the variation trends of the kH/kD values with X. The degree of bond formation in the TS is really extensive taking into account the very small values of the DKIEs. The steric effects of the two ligands on the rates are extensively discussed for the aminolyses of the chlorophosphate-type substrates on the basis of the Taft equation.

Kinetics and mechanism of the anilinolysis of diisopropyl chlorophosphate in acetonitrile

The nucleophilic substitution reactions of diisopropyl chlorophosphate (3) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 55.0 oC. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse (kH/kD = 0.71-0.95) with maximum magnitude at X = H. A concerted mechanism involving predominant backside nucleophilic attack is proposed on the basis of the secondary inverse DKIEs.

Kinetics and mechanism of the anilinolysis of ethylene phosphorochloridate in acetonitrile

The nucleophilic substitution reactions of ethylene phosphorochloridate (1c) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonit

Kinetics and mechanism of the aminolysis of aryl ethyl chloro and chlorothio phosphates with anilines

The reactions of ethyl Y-phenyl chloro (1) and chlorothio (2) phosphates with X-anilines in acetonitrile at 55.0 °C are studied kinetically and theoretically. Kinetic results yield the primary kinetic isotope effects (k H/kD = 1.07-1.80 and 1.06-1.27 for 1 and 2, respectively) with deuterated aniline (XC6H4ND2) nucleophiles, and the cross-interaction constants ρXY = -0.60 and -0.28 for 1 and 2, respectively. A concerted mechanism involving a partial frontside attack through a hydrogen-bonded, four-center-type transition state is proposed. The large ρX (ρnuc = -3.1 to -3.4) and βX (βnuc = 1.1-1.2) values seem to be characteristic of the anilinolysis of phosphates and thiophosphates with the Cl leaving group. Because of the relatively large size of the aniline nucleophile, the degree of steric hindrance could be the decisive factor that determines the direction of the nucleophilic attack to the phosphate and thiophosphate substrates with the relatively small-sized Cl leaving group. This journal is The Royal Society of Chemistry.

Quantitative structure-activity relationship of a series of N-aryl O- aryl phosphoramidate insecticides

A series of O-ethyl O-aryl N-aryl phosphoramidates was prepared and examined for housefly contact toxicity and acetylcholinesterase (ACHE) inhibition. Results showed a moderate toxicity and enzyme inhibition effect. These biological properties correlated