15081-00-2Relevant academic research and scientific papers
CuCl/bpy-promoted unusual Z-stereoselective synthesis of trichloroacetic acid phenyl ester for Hirshfeld surface analysis and DFT study
Tittal, Ram Kumar,Ram, Ram Nath,Nirwan, Ayushi,Ghule, Vikas D.,Kumar, Satish
, p. 300 - 309 (2019/03/12)
A trichloromethyl ester devoid of suitably substituted C[dbnd]C bond, any leaving group or a H-atom at the β-position to the radical, which are otherwise known for ATRA/ATRC, 1,2-rearrangement/fragmentation or simple 1,2-H shift respectively, in a reaction of trichloro-acetic acid phenyl ester with 2 mol equiv CuCl/bpy in reflux DCE or benzene under inert N2 condition resulted to stereoselective synthesis of Z-2,3-dichloro-but-2-enedioic acid diphenyl ester and/or formation of reductive de-chlorination side product. The Z-stereochemistry of the product was confirmed by X-ray diffraction spectroscopy of Z-2,3-dichloro-but-2-enedioic acid dinaphthalen-1-yl ester which crystalizes in monoclinic system of P21/c symmetry elements. Hirshfeld surface analysis of experimentally established structure of Z-2,3-dichloro-but-2-enedioic acid diphenyl ester unrevealed the intermolecular interactions showing both H-bonding and short contacts. The stereochemistry was also interpreted computationally using Density Functional Theory at B3LYP/6-311G(d,p) level of theory. The calculated energies, energy gap and balance between the electrostatic potential on the molecular surface were computed which revealed unusual formation of less stable Z-isomer.
Solvent effect and proton inventory in the hydrolysis of p-methylphenyl trichloroacetate
Frasson, Clea M.L.,Brandao, Tiago A.S.,Zucco, Cesar,Nome, Faruk
, p. 143 - 147 (2007/10/03)
Hydrolysis of p-methylphenyl trichloroacetate in water-acetonitrile mixtures was studied as a function of water concentration in the range 5.5-55.5 M. The proton inventory technique, in H2O-D2O mixtures, shows, for a value of D atom fraction in the solvent n = 0.5, deviations from the expected value (for a reaction with one proton being transferred) of 7.5 and 12.3%, for experiments in the presence of 16.6 and 33.3 M L2O (L = H or D), respectively. Theoretical treatment of the data obtained at [L 2O] = 16.6 M using the Gross-Butler equation are consistent with a cyclic transition-state structure with three protons involved. Conversely, similar experiments in the presence of [L2O] = 33.3 M show that multiple water molecules are involved in the transition state of the reaction. Copyright
