Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Photochemistry and Thermochemistry of Picolyl Chlorides

  • Shim, Sang-Chul (Department of Chemistry, Korea Advanced Institute of Science and Technology) ;
  • Kim, Sung-Sik (Department of Chemistry, Korea Advanced Institute of Science and Technology)
  • Published : 1982.09.30
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Abstract

Thermochemistry and photochemistry of picolyl chlorides were studied. The thermal reaction of 2-picolyl chloride in benzene afforded intermolecular condensation product. In the case of 3-picolyl chloride, this type of the reaction did not occur, but polymers were obtained. A cyclic hexamer, suggested by a molecular model, was not formed because of the steric strain and low reactivity. The thermal reaction of 4-picolyl chloride gave a cyclic hexamer as well as a polymer. The cyclic hexamer, identified by NMR spectrum, showed ${\lambda}_{max}$ at 460 nm. The cyclic hexamer was cloven to the linear structure. Photolysis of 2-picolyl chloride at 253.7 nm gave a para-isomer followed by polymerization. When a methyl hydrogen of 2-methylpyridine is substituted by $CH_3O$, iso-PrO, and EtO group, the photoisomerization to the corresponding anilines or para-substituted pyridines did not occur within the range of the time used for 2-picolyl chloride. Thermolysis of picolyl chlorides in an acidic methanol solution did not afford any product.

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