1,4,5,8-Tetrathiatetralin, a tetrathiafulvalene isomer
1,4,5,8-Tetrathiatetralin, a tetrathiafulvalene isomer
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1,4,5,8-四硫四氢化萘，四硫富瓦烯异构体
DOI：
10.1021/jo00870a051
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发表时间：
1976
影响因子：
3.6
通讯作者：
A. Garito
中科院分区：
文献类型：
--
作者：
M. Mizuno;M. Cava;A. Garito
先生道：四硫富瓦烯（1）及其硒类似物是制备具有金属性质的电荷转移盐的重要给体，因此一直受到人们的极大关注。1迄今未知的1，4，5，8-四硫四氢化萘（2）2是1的异构体，其结构上与后者的不同之处仅在于两个乙炔桥的排列。我们现在报告的第一个合成2和一些物理和电化学性质的这种物质。二硫化碳经电化学还原为二阴离子3，3，然后用1，2-二溴乙烷烷基化，得到（18%）三硫代碳酸酯4，为金色板，熔点121.5-122.5 ℃. 4用热的乙醇氢氧化钾水解，再与1，2-二溴乙烷烷基化，得到70%的2的四氢衍生物5，为白色针状，熔点154-156 ℃。化合物5通过在二甲苯中与DDQ反应过夜脱氢，经硅胶色谱得到2的二氢衍生物6（45%），为淡黄色针状物，熔点80-81 ℃，以及2本身（37%），为柠檬黄色针状物：熔点125-126 ℃; Xmax环己烷235 nm（e 8000），248（sh，6100），270虽然2可以被视为潜在的芳族14-7-电子体系，但其NMR光谱（CDCl 3）显示在6.46ppm处的单峰，该位置非常接近于（6.55）的烯属质子，其二氢衍生物6。这一观察结果表明，2，像母体单环类似物p-二噻英，4缺乏芳香稳定性，因此，可能具有非平面构象。
Sir: Tetrathiafulvalene (1) and its selenium analogs have been the subject of great interest, since they are valuable tt donors in the preparation of charge-transfer salts having metallic properties. 1 The hitherto unknown 1, 4, 5, 8-tetrathiatetralin (2) 2 is an isomer of 1 which differs structurally from the latter only in the arrangement of the two ethyne bridges. We now report the first synthesis of 2 and some physical and electrochemical properties of this substance. Electrochemical reduction of carbon disulfide to the dianion3, 3 followed by alkylation with 1, 2-dibromoethane, gave (18%) trithiocarbonate 4 as golden plates, mp 121.5-122.5 C. Hy-drolysis of 4 by hot ethanolic potassium hydroxide, followed by alkylationwith 1, 2-dibromoethane, gave (70%) the tetra-hydro derivative 5 of 2 as white needles, mp 154-156 C. Compound 5 was dehydrogenated by refluxing overnight with DDQ in xylene to give, after silica chromatography, the dihydro derivative 6 of 2 (45%) as pale yellow needles, mp 80-81 C, as well as 2 itself (37%) in the form of lemon yellow needles: mp 125-126 C; Xmaxcyclohexane 235 nm (e 8000), 248 (sh, 6100), 270 (sh, 5000).Although 2 may be viewed as a potentially aromatic 14-7-electron system, its NMR spectrum (CDCI3) shows a singlet at 6.46 ppm, a position very close to that (6.55) of the olefinic protons, of its dihydro derivative 6. This observation suggests that 2, like the parent monocyclic analog p-dithiin, 4 lacks aromatic stabilization and thus, may possess a nonplanar conformation.