The Chemistry of α-Oxo Ketene Cyclic Dithioacetals(X) --Studies on the Orientation of Acid Catalyzed Reaction to the Adducts of α-Oxo Ketene Cyclic Dithioacetals with Allyl Grignard Reagents

Chem. J. Chinese Universities ›› 1993, Vol. 14 ›› Issue (11): 1538.

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The Chemistry of α-Oxo Ketene Cyclic Dithioacetals(X) --Studies on the Orientation of Acid Catalyzed Reaction to the Adducts of α-Oxo Ketene Cyclic Dithioacetals with Allyl Grignard Reagents

LIU Qun¹, ZHU Zai-Ming¹, YANG Zhi-Yun¹, HU Yu-Lan¹, JING Feng-Ying², XIAO Yan-Wen²

1. Department of Chemistry, Northeast Normal University, Changchun, 130024;
2. Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun

Received:1992-12-12 Revised:1993-06-23 Online:1993-11-24 Published:1993-11-24

Abstract

Abstract: Addition of aliphatic title compounds 2b with 2-methyl allyl Grignard reagent afforded the corresponding carbinols 3b.Catalyzed by BF₃ · Et₂O, 3b were converted to the arylthio ether 5b via a cyclization-aromatization process.When water or methanol was present in the reaction mixture, 3b were converted to the phenols or arylether 5'b via a substitution-cyclization aromati-zation process under similar conditions as above.The adducts 4 formed by the addition of 2 with magnesium allyl bromide, were converted to the conjugate polyenes 6 under the above conditions either in the presence or in the absence of the nucleophile.The mechanism was discussed according to the effects of different dialkylthio groups to the carbon cation intermediates 12, 13 and 14.

Key words: α-Oxo ketene dithioacetal, Allyl Grignard reagent, Adduct, Acid catalysis, Reaction orientation

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LIU Qun, ZHU Zai-Ming, YANG Zhi-Yun, HU Yu-Lan, JING Feng-Ying, XIAO Yan-Wen. The Chemistry of α-Oxo Ketene Cyclic Dithioacetals(X) --Studies on the Orientation of Acid Catalyzed Reaction to the Adducts of α-Oxo Ketene Cyclic Dithioacetals with Allyl Grignard Reagents[J]. Chem. J. Chinese Universities, 1993, 14(11): 1538.

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The Chemistry of α-Oxo Ketene Cyclic Dithioacetals(X) --Studies on the Orientation of Acid Catalyzed Reaction to the Adducts of α-Oxo Ketene Cyclic Dithioacetals with Allyl Grignard Reagents

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