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Chinese Journal of Organic Chemistry >

2012 , Vol. 32 >Issue 12: 2334 - 2338

DOI: https://doi.org/10.6023/cjoc201207030

Notes

Intramolecular Oxidative Coupling Reaction of 4-Phenylmethyl-ene-3-isochromanones with 2,3-Dichloro-5,6-dicyanobenzo- quinone as an Oxidant

  • Ji Derong ,
  • Su Lidan ,
  • Zhang Chenggang
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  • a College of Chemistry and Mateials, Sichuan Normal University, Chengdu 610066;
    b Key Laboratory of Advanced Functional Materials, Sichuan Province Higher Education System, Chengdu 610066

Received date: 2012-07-20

  Revised date: 2012-08-28

  Online published: 2012-09-03

Supported by

Project supported by the Department of Education of Sichuan Province (No. 12ZA141) and the Key Laboratory of Advanced Functional Materials of Sichuan Province Higher Education System (No. KFKT2013-01).

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Abstract

Polymethoxy-substituted phenanthrene-9-carboxylic acid or methylate is key intermediate for synthesis of tylophora alkaloids. (E)-4-(3,4-Dimethoxybenzylidene)-6,7-dimethoxy-1H-isochromen-3(4H)-one (6), oxided by 2,3-dichloro- 5,6-dicyanobenzoquinone (DDQ)/CH3SO3H in CH2Cl2, gave no polymethoxy-substituted phenanthrene derivative (1) but unexpected 3-(2-(hydroxymethyl)-4,5-dimethoxyphenyl)-6,7-dimethoxy-2H-chromen-2-one (2) and 4,5-dimethoxy-2-(6,7-dimethoxy-2-oxo-2H-chromen-3-yl)benzaldehyde (3). Further experiments showed that the steric hindrance of a ring of isochromen-3-one (6) resulted in coumarin (2) not phenanthrene derivative (1), supported by comparative experiments of 2,3-diphenylacrylic acid (10, 12). The possible mechanism of 2 via radical cation and 3 through oxidation of precursor of 2 was proposed based on the result of experiments.

Key words： polymethoxylphenanthrene; 3-isochromanone; 3-phenylcoumarin; cross dehydrogenative coupling (CDC); radical cation; intramolecular oxidative coupling; DDQ

Cite this article

Ji Derong , Su Lidan , Zhang Chenggang . Intramolecular Oxidative Coupling Reaction of 4-Phenylmethyl-ene-3-isochromanones with 2,3-Dichloro-5,6-dicyanobenzo- quinone as an Oxidant[J]. Chinese Journal of Organic Chemistry, 2012 , 32(12) : 2334 -2338 . DOI: 10.6023/cjoc201207030

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