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| - Solid-State Solvolysis of Thiophene-Substituted Trityl-TypeAlcohols: Nucleophilic Substitution Induced by Gas−SolidContact
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| - The nucleophilic substitution reaction by gas−solid contact has been investigated. When 9-thienothienylfluoren-9-ol derivatives were coground with dichlorodicyanoquinone (DDQ) and then exposedto methanol vapor, the corresponding 9-methoxyfluorenes were obtained in 15−70% yields.Throughout the whole procedure the solid state was retained. The generation of a radical cation inthe coground solids via charge-transfer interaction between the substrate alcohol and DDQ wassuggested by the ESR spectrum. The mechanism involving the collapse of the radical cation togenerate a proton, which acts as a catalyst to afford the carbocation, was deduced based on theelectrochemical oxidation of the substrate in solution. The propagation of the substitution reactionin the solid state has been shown for the carbocation upon contact with methanol vapor. Thecrystalline inclusion compounds of 9-thienothienylfluoren-9-ol derivatives incorporating methanolas a guest were exposed to HCl gas. This gas−solid reaction also led to the formation of thecorresponding methoxy compounds maintaining the solid state. Through this work a newconsequence of solid-state cogrinding is deduced.
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