Formation of 2-phenylselenenylenones and 2-haloenones from enones. Mechanistic and synthetic aspects, X-ray crystal structures of intermediates

作者: Lars Engman , Karl Wilhelm Törnroos

DOI: 10.1016/0022-328X(90)80171-U

关键词: PhotochemistryChemistryDouble bondHaloketoneDiffractionCrystal structureComputational chemistryMoleculePyridineX-rayX-ray crystallography

摘要: Abstract The structure of trans-3-chloro-2-phenylselenenylcyclohexanone (1) was determined by X-ray diffraction. Although this and similar compounds were readily dehydrohalogenated to give vinylic selenides, they ruled out as intermediates in the synthesis 2-phenylselenenylenones from enones 1:1 complex PhSeCl pyridine. 2-Phenylselenenylenones halogenated treatment with SO2Cl2 or Br2 unstable products 1,2-addition double bond. trans-2,3-dichloro-2-phenylselenenylcyclohexanone (5) Since compound does not lose a molecule solution, it considered be unlikely an intermediate PhSeCl·pyridine induced conversion 2-cyclohexenone 2-chloro-2-cyclohexenone. However, upon phenylselenenylenones presence pyridine, rapid formation corresponding α-chloroenone observed under mild conditions.

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