The synthesis of some thiophenophanes and attempted cyclisations to polycyclic thiophenium salts

The synthesis of some thiophenophanes and attempted cyclisations to polycyclic thiophenium salts
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一些噻吩烷的合成并尝试环化为多环噻吩鎓盐

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发表时间：
1987
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影响因子：
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通讯作者：
Gary C. M. Lee
Gary C. M. Lee
中科院分区：
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文献类型：
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作者：
R. Acheson;Gary C. M. Lee

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合成了5，10-二苯基环十三碳-2，4，10，12-四烯-6，8-二炔-1-酮（28）、5，6，7，8-四氢二苯并[a，g]环十三碳烯-15-酮（21）和13，14，16，17-四氢-5，6，7，8-四脱氢二苯并[a，g]环十三碳烯-15-酮（40）。所有试图将硫化氢加到这些化合物的三键上得到噻吩的尝试都失败了。以1，5-二（2-乙炔基苯基）戊-3-酮（36）为原料，经醋酸铜氧化合成了13，14，16，17-四氢-5，8-环硫代二苯并[a，g]环十三烯-1,5-酮（43）。这种酮是由2-碘苯甲醛得到的，2-碘苯甲醛依次用丙酮和乙炔基三甲基硅烷处理得到1，5-双（2-三甲基甲硅烷基乙炔基苯基）戊-1，4-二烯-3-酮（18）。氢化三丁基锡仅还原该酮中的乙烯基双键，随后水解得到酮（36）。用硼氢化钠还原环状酮（40）得到醇（41），硫化钠将二炔基团转化为噻吩环得到噻吩醇（42），铬酸现在得到酮（43）。尝试将该醇（42）和酮（43）转化成五环锍盐或相关化合物导致氧的消除和烯烃的形成。
5,10-Diphenylcyclotrideca-2,4,10,12-tetraene-6,8-diyn-1-one (28), 5,6,7,8-tetrahydrodibenzo[a,g]cyclotridecen-15-one (21), and 13,14,16,17-tetrahydro-5,6,7,8-tetradehydrodibenzo[a,g]cyclotridecen-15-one (40) were synthesized. All attempts to add hydrogen sulphide across the triple bonds of these compounds to give thiophenes failed. 13,14,16,17-Tetrahydro-5,8-epithiodibenzo[a,g]cyclotridecen-15-one (43), from which hydrogen sulphide was removed by DDQ or chloroanil to give the ketone (40), was synthesized via the copper(II) acetate oxidation of 1,5-bis(2-ethynylphenyl)pentan-3-one (36). This ketone was obtained from 2-iodobenzaldehyde which on successive treatment with acetone, and ethynyltrimethylsilane yielded 1,5-bis(2-trimethylsilylethynylphenyl)penta-1,4-dien-3-one (18). Tributyltin hydride reduced the vinyl double bonds only in this ketone, and subsequent hydrolysis gave the ketone (36). Reduction of the, cyclic ketone (40) with sodium borohydride gave the alcohol (41), sodium sulphide converted the diyne grouping into a thiophene ring giving the thiophene alcohol (42), and chromic acid now yielded the ketone (43). Attempts to convert this alcohol (42) and ketone (43) into pentacyclic sulphonium salts or related compounds resulted in elimination of oxygen and the formation of olefins.