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Title: Synthesis of 2,5-Disubstituted Thienosultines and Their Thermal Reactions with Dienophiles and Nucleophiles
Authors: Liu, Wen-Dar;Chi, Chih-Chin;Pai, I-Feng;Wu, An-Tai;Chung, Wen-Sheng
Contributors: 化學系
Date: 2002-12
Issue Date: 2013-01-07T01:47:33Z
Publisher: American Chemical Society
Abstract: The 2,5-disubstituted thienosultines (5,7-disubstituted 1,4-dihydro-1H-3lambda(4)-thieno[3,4-d][2,3]oxathiin-3-oxides) 5a-d were prepared from the corresponding dichlorides 4a-d with the commercially available Rongalite (sodium formaldehyde sulfoxylate) in 17-60% yields. When heated in the presence of electron-poor dienophiles, sultines 5a-d underwent elimination of SO(2), and the resulting non-Kekul� biradicals 7a-d were intercepted as the 1:1 adducts 8-12 in good to excellent yields. The pyrolysis of sultines and sulfolenes with different concentrations of dienophiles revealed that either a preequilibrium between starting reagents and biradical species or Diels-Alder and retro-Diels-Alder reaction mechanisms may be involved; however, more work is necessary to establish the proposed mechanisms. Reaction of sultine 5b with nBuLi was found to undergo a nucleophilic ring-opening reaction to give sulfinyl alcohol 17 after H(2)O workup. When sultine 5a was heated in benzene in a sealed tube in the presence of methanol, methanol-d(4), or 2-mercaptoethanol, the respective 1:1 trapping adducts 19-21 as well as the rearranged sulfolene 6a were isolated in similar amounts. The isolation of adducts 19-21 may be explained by the involvement of either biradical or ionic intermediates during the pyrolysis.
Relation: J. Org. Chem., 67(26): 9267-9275
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