7515-28-8Relevant articles and documents
Solvent and structural effects on the kinetics of the reactions of 2-substituted cyclohex-1-enylcarboxylic and 2-substituted benzoic acids with diazodiphenylmethane
Nikolic,Uscumlic,Juranic
, p. 664 - 671 (2007)
The rate constants for the reaction of 2-methyl-cyclohex-1-enylcarboxylic, 2-phenylcyclohex-1-enylcarboxylic, and 2-methylbenzoic and 2-phenylbenzoic acids with diazodiphenyl-methane were determined in 14 various solvents at 30°C. To explain the kinetic results through solvent effects, the second-order rate constants of the examined acids were correlated using the Kamlet-Taft solvatochromic equation. The correlations of the kinetic data were carried out by means of multiple linear regression analysis, and the solvent effects on the reaction rates were analyzed in terms of initial and transition state contributions. The quantitative relationship between the molecular structure and the chemical reactivity has been discussed, as well as the effect of geometry on the reactivity of the examined molecules. The geometric data of all the examined compounds corresponding to the energy minima in solvent, simulated as dielectric continuum, obtained using semiempirical MNDO-PM3 energy calculations.
Hydrogen-bond-assisted transition-metal-free catalytic transformation of amides to esters
Huang, Changyu,Li, Jinpeng,Wang, Jiaquan,Zheng, Qingshu,Li, Zhenhua,Tu, Tao
, p. 66 - 71 (2020/11/18)
The amide C-N cleavage has drawn a broad interest in synthetic chemistry, biological process and pharmaceutical industry. Transition-metal, luxury ligand or excess base were always vital to the transformation. Here, we developed a transition-metal-free hydrogen-bond-assisted esterification of amides with only catalytic amount of base. The proposed crucial role of hydrogen bonding for assisting esterification was supported by control experiments, density functional theory (DFT) calculations and kinetic studies. Besides broad substrate scopes and excellent functional groups tolerance, this base-catalyzed protocol complements the conventional transition-metal-catalyzed esterification of amides and provides a new pathway to catalytic cleavage of amide C-N bonds for organic synthesis and pharmaceutical industry. [Figure not available: see fulltext.]
Palladium-Catalyzed Carbonylative Synthesis of Benzyl Benzoates Employing Benzyl Formates as Both CO Surrogates and Benzyl Alcohol Sources
Lai, Ming,Qi, Xinxin,Wu, Xiao-Feng
supporting information, p. 3776 - 3778 (2019/06/24)
An efficient and convenient palladium-catalyzed carbonylation reaction for the synthesis of benzyl benzoates from aryl bromides has been developed. Benzyl formates have been explored as a new type of efficient and useful CO sources and also reaction partners. A wide range of benzyl benzoates was obtained in good to excellent yields.
