18133-58-9Relevant articles and documents
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.
Selectivity of the Aromatic Plumbylation Reaction
Stock, Leon M.,Wright, Terry L.
, p. 4645 - 4648 (2007/10/02)
The plumbylation of toluene in dichloroacetic acid yields initially 5.4percent 2-, 1.8percent 3-, and 92.7percent 4-methylphenyllead(IV) dichloroacetates.The toluene to benzene rate ratio under these conditions is 59.9.The partial rate factors are oMef = 9.64, mMef = 3.21, pMef = 331.The plumbylation of toluene in trifluoroacetic acid yields aryl trifluoroacetates and biaryls.Analysis of these products suggest that the plumbylation reaction yields 17.9percent 2-, 3.2percent 3-, and 78.9percent 4-methylphenyllead (IV) trifluoroacetates in the initial step of the reaction.The toluene to benzene rate ratio is 114 under these conditions.The partial rate factors are oMef = 61.2, mMef = 10.8, and pMef = 540.These observations suggest that the plumbylation reaction is a typical electrophilic substitution and that the reaction is significantly more selective than thallation or mercuration.
