The Chemistry of α-Oxo Ketene Cyclic Dithioacetals(XXII)--Substitution Cycloaromatization Reaction of α-Oxoketene Dithioacetals with Methallyl Grignard Reagent Using Mercaptan as the Nucleophiles

Chem. J. Chinese Universities ›› 1995, Vol. 16 ›› Issue (7): 1047.

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The Chemistry of α-Oxo Ketene Cyclic Dithioacetals(XXII)--Substitution Cycloaromatization Reaction of α-Oxoketene Dithioacetals with Methallyl Grignard Reagent Using Mercaptan as the Nucleophiles

LIU Qun, XU Bai-Ling, YANG Zhi-Yun, ZHAO Hong-Wu

Dept. of Chem., Northeast Normal Univ., Changchun, 130024

Received:1994-07-27 Revised:1994-12-18 Online:1995-07-24 Published:1995-07-24

Abstract

Abstract: The 1,2-addition of α-oxoketene dithioacetals with methallyl Grignard reagent afforded the carbinols 2. 5 and 6 respectively. Catalyzed by sulfuric acid, 2 and 5 were converted to the same product (such as 3_c)3 (or 4) when mercaptan (or phenyl-sulfohydrate) was used as the nucleophile. The above conversion was believed to proceed via a substitution cyclo aromatization mechanism. Under the same condition, compound 6 was converted to the cycloaromatization product 7. Based on the experimental facts, a reactivity order 1,3-propy-lenedithio>1,2-ethylenedithio>dimethylthio was proposed to the substitution cycloaromatization reaction.

Key words: α-Oxoketene dithioacetal, Methallyl Grignard reagent, Adduct, Mercaptan, Substitution cycloaromatization reaction

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LIU Qun, XU Bai-Ling, YANG Zhi-Yun, ZHAO Hong-Wu . The Chemistry of α-Oxo Ketene Cyclic Dithioacetals(XXII)--Substitution Cycloaromatization Reaction of α-Oxoketene Dithioacetals with Methallyl Grignard Reagent Using Mercaptan as the Nucleophiles[J]. Chem. J. Chinese Universities, 1995, 16(7): 1047.

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The Chemistry of α-Oxo Ketene Cyclic Dithioacetals(XXII)--Substitution Cycloaromatization Reaction of α-Oxoketene Dithioacetals with Methallyl Grignard Reagent Using Mercaptan as the Nucleophiles

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