α-Oxothiones, IV: Electrophilic substitution of phenols with α,α′-dioxothiones and ortho-thioquinones

European Journal of Organic Chemistry

Volumn , Issue 21, 2000, Pages 3653-3657

  Capozzi, Giuseppe ^a   Menichetti, Stefano ^b   Nativi, Cristina ^a  

^a UNIVERSITY OF FLORENCE   (Italy)

^b UNIVERSITY OF MESSINA   (Italy)

Author keywords

Electrophilic aromatic substitution; Regioselectivity; Sulfides; Sulfur; Thioketones; Thioquinones

Indexed keywords

PHENOL DERIVATIVE; QUINONE DERIVATIVE; THIOKETONE;

ARTICLE; CHEMICAL INTERACTION; CHEMICAL REACTION; CHEMICAL STRUCTURE; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0033762771     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/1099-0690(200011)2000:21<3653::aid-ejoc3653>3.0.co;2-0     Document Type: Article

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16. Several other electron-rich arenes tested - such as, among others, 1,3-dimethoxybenzene, anthracene, and aniline - were unreactive towards thione 1a.
17. In the case of sulfide 17, the attribution of the relative regiochemistry was also achieved by comparison with the result observed in the same reaction with ortho-thioquinone 2a (vide infra).
18. Chloroform and dichloromethane are the best solvents for these reactions. Benzene, THF, acetone, acetonitrile, and DMSO cause a remarkable decrease in the reaction rate, while with DMF we observed only polymerization of the thione 1a.
19. Generation of thione 1a with TEA or DBU in the presence of phenol 9, resulted in a drastic decrease in the reaction yield.
20. In the reaction of 2a with m-methoxyphenol, we also isolated the corresponding bis-substituted derivative 25 (6%). (Chemical Equation Presented)
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