6533b851fe1ef96bd12a8e1a

RESEARCH PRODUCT

A new potential toxaphene congener: synthesis, GC/EI-MS study, crystal structure, NMR analysis, and ab initio calculations of 3-endo,5-endo-dichloro-7,7-bis-chloromethyl-4-dichloromethyl-tricyclo[2.2.1.02,6]heptane

subject

description

Abstract A new potential toxaphene congener 3- endo ,5- endo -dichloro-7,7-bis-chloromethyl-4-dichloromethyl-tricyclo[2.2.1.0 2,6 ]heptane 2 has been isolated from reaction mixture obtained by the chlorination of 2- exo ,10,10-trichlorobornane 1 . The X-ray structural analysis of 2 revealed an unusual tricyclic structure, where the two chlorine atoms occupying endo -positions are in close spatial proximity with each other and near to the neighbouring CHCl 2 group. Further, it revealed that the symmetry of the molecule is distorted. The 1 H and 13 C NMR spectra of 2 have been assigned by means of 1 H, 1 H d ouble- q uantum f iltered co rrelation s pectroscop y (DQF COSY), PFG 1 H, 13 C HMQC ( p ulsed f ield g radient h eteronuclear m ultiple- q uantum c oherence), 1 H, 13 C h eteronuclear m ultiple b ond c orrelation (HMBC) experiments, and computer aided 1 H NMR spectral analysis. The asymmetry of 2 is also discernible on the 1 H NMR parameters. In addition, gas chromatographic (GC) properties and electron impact (EI) mass spectrum of 2 has been studied. Ab initio Hartree–Fock (HF) method with the basis set 6–31G(d) has been used for the optimization of the equilibrium geometry and calculation of total energy for 2 . The optimized geometry is in good agreement with the crystal structure. According to the rotation energy profile calculated at the HF/6–31G(d) level, rotation of the chloromethyl and dichloromethyl groups are highly unlikely at the room temperature.