The first synthesis and properties of 2,3-di-t-butylthiophene. Reaction of 3,4-di-t-butyl-1,2-dithiete with dimethyl acetylenedicarboxylate.

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概要

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• Heating 3,4-di-<I>t</I>-butyl-1,2-dithiete (<B>5</B>) with dimethyl acetylenedicarboxylate (5 equiv) in refluxing <I>o</I>-dichlorobenzene affords dimethyl 2,5-di-<I>t</I>-butyl-3,4-thiophenedicarboxylate (<B>6</B>) (44%), dimethyl 2,3-di-<I>t</I>-butyl-4,5-thiophenedicarboxylate (<B>7</B>) (5%), tetramethyl 1,4-dithiin-2,3,5,6-tetracarboxylate (<B>8</B>) (4%), and tetramethyl 2,3,4,5-thiophenetetracarboxylate (<B>9</B>) (43%). Mechanism of the formation of these products is discussed. Treatment of the hindered ester <B>7</B> with lithium 1-propanethiolate affords 2,3-di-<I>t</I>-butyl-4,5-thiophenedicarboxylic acid (<B>13</B>) in 59% yield, which can be decarboxylated by treatment with copper powder to give 2,3-di-<I>t</I>-butylthiophene (<B>4</B>) in 88% yield. The thiophene <B>4</B> rearranges to 2,4-di-<I>t</I>-butylthiophene (<B>1</B>) on treatment with aluminum chloride. Oxidation with <I>m</I>-CPBA affords the corresponding sulfone (<B>23</B>). Electrophilic substitutions (bromination and nitration) of <B>4</B> occur exclusively at the less hindered and more electronically favored 5-position.

• 公益社団法人 日本化学会の論文

著者

• Ishii Akihiko

  Department Of Chemistry Faculty Of Science Saitama University

• Nakayama Juzo

  Department Of Chemistry Faculty Of Science Saitama University

• Choi Keun

  Department Of Mechanical Engineering School Of Mechanical Aerospace & Systems Engineering Korea

• Hoshino Masamatsu

  Department of Chemistry, Faculty of Science and Engineering, Saitama University

• Choi Keun

  Department of Chemistry, Faculty of Science, Saitama University

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