PARTIALLY FLUORINATED HETEROCYCLIC-COMPOUNDS .27. THE SYNTHESIS OF 4,5,6,7-TETRAFLUOROBENZO[C]THIOPHENE AND 4,5,6,7,8,9-HEXAFLUORONAPHTHO[1,2-C]THIOPHENE - SOME CHEMISTRY AND ELECTROCHEMISTRY
PARTIALLY FLUORINATED HETEROCYCLIC-COMPOUNDS .27. THE SYNTHESIS OF 4,5,6,7-TETRAFLUOROBENZO[C]THIOPHENE AND 4,5,6,7,8,9-HEXAFLUORONAPHTHO[1,2-C]THIOPHENE - SOME CHEMISTRY AND ELECTROCHEMISTRY
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DOI：
10.1039/p19900001919
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发表时间：
1990-07-01
期刊：
影响因子：
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通讯作者：
MAWSON, SD
中科院分区：
文献类型：
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作者：
BROOKE, GM;MAWSON, SD
2,3,4,5,6-五氟苯甲酰亚砜(6)很容易被丁基锂转化为4,5,6,7-四氟苯并[c]噻吩(8)和1,3,4,5,6,7,8-七氟-2-萘甲基甲基亚砜(9)，以类似的方式得到非常低的产率4,5,6,7,8-六氟萘[1,2-c]噻吩（11），分别伴有7-和8-丁基化衍生物（12）和（13），以及1,3,4,5,6,7,8-七氟萘-2-乙醛（10）。化合物(8)经过Diels-Alder加成反应，然后与二甲基乙炔二羧酸酯和四氟苯酶消除硫，分别得到萘和蒽衍生物（14）和（15）。化合物(8)与丙烷-2-硫酸锂结合，分别得到5-丙-2-基硫和5,6-双丙-2-基硫衍生物（16）和（17）。化合物(8)被SbF5-HF聚合成聚（1,3-二氢-4,5,6,7-四氟苯并[c]-噻吩）（20）。(8)的电化学阳极氧化已经得到了广泛的研究：聚合物（20）的产生伴随着一种深红色的易溶于氯仿的物质，这不是聚（4,5,6,7-四氟苯并[c]噻吩）（24）。
2,3,4,5,6-Pentafluorobenzyl methyl sulphoxide (6) is readily converted by butyl-lithium into 4,5,6,7-tetrafluorobenzo[c]thiophene (8) and 1,3,4,5,6,7,8-heptafluoro-2-naphthylmethyl methyl sulphoxide (9) in a similar manner gives a very low yield of 4,5,6,7,8,9-hexafluoronaphtho[1,2-c]thiophene (11) accompanied by the 7- and 8-butylated derivatives (12) and (13) respectively, and also 1,3,4,5,6,7,8-heptafluoronaphthalene-2-carbaldehyde (10). Compound (8) undergoes Diels–Alder addition reactions followed by sulphur elimination with dimethyl acetylenedicarboxylate and tetrafluorobenzyne to give the naphthalene and anthracene derivatives (14) and (15) respectively. With lithium propane-2-thiolate, compound (8) gives the 5-propan-2-ylthio and 5,6-bispropan-2-ylthio derivatives (16) and (17) respectively. Compound (8) is polymerisedby SbF5–HF to poly(1,3-dihydro-4,5,6,7-tetrafluorobenzo[c]-thiophene)(20). The electrochemical anodic oxidation of (8) has been studied extensively: polymer (20) is produced accompanied by a deep red material readily soluble in chloroform, which is not poly(4,5,6,7-tetrafluorobenzo[c]thiophene)(24).