306743-67-9

Upstream product

• 118-90-1 ortho-methylbenzoic acid 
• 99-93-4 4-Hydroxyacetophenone 
• 73686-46-1 2-methylbenzoic acid 2-pyridinyl ester 
• 933-88-0 ortho-toluoyl chloride 

Downstream Products

• 33388-67-9 (2-methyl-phenyl)-(piperidin-1-yl)methanone 

Relevant academic research and scientific papers

Transesterification of (hetero)aryl esters with phenols by an Earth-abundant metal catalyst

Readily available and inexpensive Earth-abundant alkali metal species are used as efficient catalysts for the transesterification of aryl or heteroaryl esters with phenols which is a challenging and underdeveloped transformation. The simple conditions and the use of heterogeneous alkali metal catalyst make this protocol very environmentally friendly and practical. This reaction fills in the missing part in transesterification reaction of phenols and provides an efficient approach to aryl esters, which are widely used in the synthetic and pharmaceutical industry.

Kinetic study on nucleophilic displacement reactions of y-substituted-phenyl 2-methylbenzoates with cyclic secondary amines in acetonitrile: Effects of modification of 2-meo in benzoyl moiety by 2-me on reactivity and reaction mechanism

The second-order rate constants (kN) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted-phenyl 2-methylbenzoates (6a-e) with a series of cyclic secondary amines in MeCN at 25.0 ± 0.1 oC. Comparison of the kN values for the reactions of 4-nitrophenyl 2-methylbenzoate (6d) with those reported previously for the corresponding reactions of 4-nitrophenyl 2-methoxybenzoate (5) reveals that 6d is significantly less reactive than 5, indicating that modification of 2-MeO in the benzoyl moiety of 5 by 2-Me (i.e., 5 ? 6d) causes a significant decrease in reactivity. This supports our previous report that aminolysis of 5 proceeds through a six-membered cyclic intermediate, which is highly stabilized through intramolecular H-bonding interactions. The Bronsted-type plot for the reactions of 6d with a series of cyclic secondary amines is linear with ssnuc = 0.71, which appears to be a lower limit of ssnuc for a stepwise mechanism with breakdown of an intermediate (T±) being rate-determining step (RDS). The Bronsted-type plot for the reactions of 6a-e with piperidine is curved, i.e., the slope of Bronsted-type plot (sslg) decreases from -1.05 to -0.41 as the leavinggroup basicity decreases. The nonlinear Bronsted-type plot has been taken as evidence for a stepwise mechanism with a change in RDS (e.g., from the k2 step to the k1 process as the leaving-group basicity decreases). Dissection of kN into the microscopic rate constants associated with the reactions of 6a-e with piperidine (e.g.,k1 and k2/k-1 ratio) also supports the proposed mechanism.

Effect of o-methyl group on rate, mechanism, and resonance contribution: Aminolysis of Y-substituted phenyl X-substituted 2-methylbenzoates

Second-order rate constants have been determined spectrophotometrically for the reactions of 4-nitrophenyl X-substituted 2-methylbenzoates (2a-e) and Y-substituted phenyl 2-methylbenzoates (3a-e) with alicyclic secondary amines in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The o-methyl group in the benzoyl moiety of 2a-e retards the reaction rate but does not influence the reaction mechanism. The Hammett plots for the reactions of 2a-e are nonlinear, while the corresponding Yukawa-Tsuno plots are linear with large r values (1.06-1.70). The linear Yukawa-Tsuno plots suggest that stabilization of the ground-state through resonance interaction between the electron donating substituent X and the carbonyl group is responsible for the nonlinear Hammett plots, while the large r values imply that the ground-state resonance interaction is significant. The reactions of 2a-e resulted in smaller ρX values but larger r values than the corresponding reactions of 4-nitrophenyl X-substituted benzoates (1a-e). The small ρX value for the reactions of 2a-e (e.g., ρX = 0.22) is suggested to be responsible for the large r value (e.g., r = 1.70). The reactions of 3a-e with piperidine are proposed to proceed in a stepwise manner with a change in the rate-determining step on the basis of the curved Bronsted-type plot obtained. Microscopic rate constants associated with the reactions of 3a-e are also consistent with the proposed mechanism.