39274-91-4

Upstream product

• 108-44-1 1-amino-3-methylbenzene 

Downstream Products

• 39274-83-4 C₇H₇⁽²⁾H₃N⁽¹⁺⁾*Cl^(1-) 
• 39274-83-4 C₇H₇⁽²⁾H₂N*Cl⁽²⁾H 

Relevant academic research and scientific papers

Concerted pathway to the mechanism of the Anilinolysis of Bis(N,N-diethylamino)phosphinic chloride in Acetonitrile

The kinetics of the nucleophilic substitution reactions of bis(N,N-diethylamino)phosphinic chloride with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated in MeCN at 65.0°C. The deuterium kinetic isotope effects (DKIEs) are secondary inverse (kH/kD1: 0.706-0.947) and the magnitudes of the secondary inverse DKIEs (kH/kD) increase constantly as the nucleophiles are changed from weakly basic to strongly basic anilines. The magnitudes of the selectivity parameters are ρX(H)≤-6.34, and βX(H)≤2.24 with substituted anilines and ρX(D)≤-6.13 and βX(D)≤2.17 with deuterated anilines. A concerted SN2 mechanism involving predominant backside attack is proposed based on the kH/kD values with substituent X.

Anilinolysis of O-butyl phenyl phosphonochloridothioate in acetonitrile: Synthesis, characterization, kinetic study, and reaction mechanism

This paper describes a simple optimized method for the synthesis of O-butyl phenyl phosphonochloridothioate (4) under mild conditions. The target compounds were characterized by 1H-nuclear magnetic resonance (NMR), 13C-NMR, and 31P-NMR spectroscopy, as well as mass spectroscopy. The apparent structure of 4 was confirmed by optimization using the B3LYP/6-311?+?G(d,p) level in the Gaussian 09 program in acetonitrile. The nucleophilic substitution reactions of 4 with X-anilines (XC6H4NH2) and deuterated X-anilines (XC6H4ND2) were investigated kinetically in acetonitrile at 55.0°C. The free energy relationship with X in the anilines looked biphasic concave upwards with a break region between X?=?H and X?=?3-MeO, giving large negative ρX and small positive βX values. The deuterium kinetic isotope effects were secondary inverse (kH/kD?H/kD), increased when the nucleophiles were changed from weakly basic to strongly basic anilines. A concerted SN2 mechanism is proposed on the basis of the selectivity parameters and the variation trend of the deuterium kinetic isotope effects with X.

Kinetics and mechanism of anilinolyses of ethyl methyl, ethyl propyl and diisopropyl chlorothiophosphates in acetonitrile

Nucleophilic substitution reactions of ethyl methyl (2), ethyl propyl (4) and diisopropyl (7) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 55.0 oC. A concerted mechanism is proposed based on the selectivity parameters. The deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse (kH/kD = 0.66-0.99) with 2, primary normal and secondary inverse (kH/ kD = 0.78-1.19) with 4, and primary normal (kH/kD = 1.06-1.21) with 7. The primary normal and secondary inverse DKIEs are rationalized by frontside attack involving hydrogen bonded, four-center-type transitionstate, and backside attack involving in-line-type transition state, respectively. The anilinolyses of ten chlorothiophosphates are examined based on the reactivity, steric effect of the two ligands, thio effect, reactionmechanism, DKIE and activation parameter.

Kinetics and mechanism of the anilinolysis of (2R,4R,5S)-(+)-2-chloro-3,4- dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide in acetonitrile

The nucleophilic substitution reactions of (2R,4R,5S)-(+)-2-chloro-3,4- dimethyl-5-phenyl-1,3,2-oxazapho-spholidine 2-sulfide (3) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 5.0 °C. The anilinolysis rate of 3 involving a cyclic five-membered ring is considerably fast because of small negative value of the entropy of activation (ΔS≠ = -2 cal mol-1 K -1) over considerably unfavorable enthalpy of activation (ΔH≠ = 18.0 kcal mol-1). Great enthalpy and small negative entropy of activation are ascribed to sterically congested transition state (TS) and bulk solvent structure breaking in the TS. A concerted S N2 mechanism with a backside nucleophilic attack is proposed on the basis of the secondary inverse deuterium kinetic isotope effects, k H/kD 1.

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 the anilinolysis of o-ethyl phenyl phosphonochloridothioate in acetonitrile

The nucleophilic substitution reactions of O-ethyl phenyl phosphonochloridothioate with substituted anilines (XC6H 4NH2) and deuterated anilines (XC6H 4ND2) are kinetically investigated in acetonitrile at 55.0 °C. The deuterium kinetic isotope effects (DKIEs) invariably increase from a secondary inverse DKIE (kH/kD = 0.93) to a primary normal DKIE (kH/kD = 1.28) as the substituent of nucleophile (X) changes from electron-donating to electron-withdrawing. These can be rationalized by the gradual transition state (TS) variation from a backside to frontside attack. A concerted SN2 mechanism is proposed. A trigonal bipyramidal TS is proposed for a backside attack while a hydrogen-bonded, four-center-type TS is proposed for a frontside attack.

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.