噻吩-3,4-二硫醇 | 87207-45-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 中文名称: 噻吩-3,4-二硫醇
• 英文名称: Thiophene-3,4-dithiol
• 英文别名: tiophene-3,4-dithiole；3,4-thiophenedithiol；Thiophen-3,4-dithiol；3,4-Bis-mercaptothiophene
• CAS: 87207-45-2
• 化学式: C₄H₄S₃
• 分子量: 148.274
• InChiKey: TWXMZYPORGXIFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  30.2
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  噻吩-3,4-二硫醇 在 四次甲氨基乙硼烷 、 盐酸 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 15.0h， 生成 2,2'-bi(1,3,5,2-trithiaborapentalene)
  参考文献：
  名称：

  Three sulfur-containing diborane(4) compounds

  摘要：

  The preparation and structures of three diborane(4) compounds ape described. The compound B-2(3,4-S2C4H2-1-S)(2)[2,2'-bi(1,3,5,2-trithiaborapentalene), C8H4B2S6] is planar and lies at a crystallographic inversion centre. The amine adducts [B-2(C3S5)(2)(NHMe2)(2)] [2,2'-bis(dimethylamino)-2,2'-bi(1,3,4,6,2-tetrathiaborapentalene-5-thione), C10H14B2N2S10] and [B-2(1,2-S2C2H4)(2)(NHMe2)(2)]. 0.33CH(2)Cl(2) [1,2-bis(dimethylamino)-1,1:2,2-bis(dimethylenedithioxy)diborane(4) dichloromethane solvate, C8H22B2N2S4. 0.33CH(2)Cl(2)] contain dimethylamine ligands bound to each boron in an anti conformation about the B-B bond, with tetrahedral geometry at the B atoms. The crystal structures display a number of S ... S interactions, which appear to dictate the packing arrangements.

  DOI：

  10.1107/s0108270199014778
• 作为产物：
  描述：

  3,4-二溴噻吩 在 正丁基锂 、 sulfur 、 盐酸 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 0.5h， 生成 噻吩-3,4-二硫醇
  参考文献：
  名称：

  Three sulfur-containing diborane(4) compounds

  摘要：

  The preparation and structures of three diborane(4) compounds ape described. The compound B-2(3,4-S2C4H2-1-S)(2)[2,2'-bi(1,3,5,2-trithiaborapentalene), C8H4B2S6] is planar and lies at a crystallographic inversion centre. The amine adducts [B-2(C3S5)(2)(NHMe2)(2)] [2,2'-bis(dimethylamino)-2,2'-bi(1,3,4,6,2-tetrathiaborapentalene-5-thione), C10H14B2N2S10] and [B-2(1,2-S2C2H4)(2)(NHMe2)(2)]. 0.33CH(2)Cl(2) [1,2-bis(dimethylamino)-1,1:2,2-bis(dimethylenedithioxy)diborane(4) dichloromethane solvate, C8H22B2N2S4. 0.33CH(2)Cl(2)] contain dimethylamine ligands bound to each boron in an anti conformation about the B-B bond, with tetrahedral geometry at the B atoms. The crystal structures display a number of S ... S interactions, which appear to dictate the packing arrangements.

  DOI：

  10.1107/s0108270199014778

文献信息

• [4+3] Cycloaddition of Donor-Acceptor Cyclopropanes with Amphiphilic Benzodithioloimine as Surrogate for <i>ortho</i> -Bisthioquinone
  作者：Lennart K. B. Garve、Martin Pawliczek、Jan Wallbaum、Peter G. Jones、Daniel B. Werz

  DOI：10.1002/chem.201504013

  日期：2016.1.11

  Donor–acceptor cyclopropanes were reacted with amphiphilic benzodithioloimine to give seven‐membered heterocycles with two sulfur atoms. Formally, this transformation can be regarded as a [4+3] cycloaddition reaction of the three‐membered ring and ortho‐bisthioquinone. The benzodithioloimine serves as a surrogate for this highly reactive diene. The structure of the products was confirmed by X‐ray crystallography

  供体-受体环丙烷与两亲性苯并二硫代次氯亚胺反应生成具有两个硫原子的七元杂环。从形式上讲，这种转变可以看作是三元环和邻双硫代醌的[4 + 3]环加成反应。苯并二硫代次氯亚胺用作该高反应性二烯的替代物。产品结构通过X射线晶体学确认。13 C NMR研究中的宽信号表明，室温下存在几个在NMR时标上缓慢相互转化的构象体。
• EPR studies on the thiophenodithiazolyl radical, C4H2S3N˙
  作者：Antonio Alberola、Robert D. Farley、Simon M. Humphrey、Gordon D. McManus、Damien M. Murphy、Jeremy M. Rawson

  DOI：10.1039/b508912c

  日期：——

  Selective chlorination of thiophene-2,3-dithiol with SO2Cl2 generates the corresponding sulfenyl chloride, 2,3-C4H2S(SCl)2. Subsequent condensation with Me3SiN3 yields the thiophenodithiazolylium salt [C4H2S3N]Cl, [TDTA]Cl. The structure of the cation, TDTA+, was established by X-ray diffraction as both its AsF6− and HSO4− salts. Reduction of [TDTA]Cl with Ag powder yields the radical TDTA˙ which was characterised by X- and Q-band (9 and 34 GHz) EPR and ENDOR studies. The spin density distributions estimated from the EPR/ENDOR measurements were found to be in very good agreement with those determined by DFT (B3LYP/6-31G*) indicating that ca 10% of the spin density is delocalised onto the thiophene ring. Comparison of the spin density distributions in TDTA˙ and the isoelectronic trithiatriazapentalenyl radical C2S3N3, TTTA˙, indicates that replacement of N by C–H leads to a localisation of the spin density on the dithiazolyl ring.

  用 SO2Cl2 对噻吩-2,3-二硫醇进行选择性氯化，可生成相应的亚磺酰氯 2,3-C4H2S(SCl)2。随后与 Me3SiN3 缩合，可生成噻吩二噻唑鎓盐 [ 3N]Cl，即 [TDTA]Cl。通过 X 射线衍射，确定了阳离子 TDTA+ 的 AsF6â 盐和 HSO4â 盐的结构。用银粉还原 [TDTA]Cl 会产生自由基 TDTAË，并通过 X 波段和 Q 波段（9 和 34 GHz）的 EPR 和 ENDOR 研究对其进行了表征。根据 EPR/ENDOR 测量结果估算出的自旋密度分布与 DFT（B3LYP/6-31G*）确定的自旋密度分布非常一致，表明约有 10% 的自旋密度被分散到噻吩环上。比较 TDTAË 和等电子三硫杂三氮杂环戊烯基 C2S3N3（TTTAË）中的自旋密度分布表明，用 CâH 替代 N 会导致自旋密度集中在二噻唑环上。
• Rasheed, Khalid; Warkentin, James D., Journal of Heterocyclic Chemistry, 1981, vol. 18, p. 1581 - 1585
  作者：Rasheed, Khalid、Warkentin, James D.

  DOI：——

  日期：——
• New π-electron donor systems based on acenaphtho[1,2-b][1,4]dithiine
  作者：Martin R. Bryce、Antony Chesney、Alexander K. Lay、Andrei S. Batsanov、Judith A. K. Howard

  DOI：10.1039/p19960002451

  日期：——

  Syntheses of the acenaphtho[1,2-b] [1,4] dithiine derivatives 12, 25 and 29 are reported. Cyclic voltammetric studies reveal that these compounds undergo reversible single-electron oxidations at < 1.0 V, vs. Ag/AgCl. Lithiation of compound 12 with BuLi (2 equiv.) followed by addition of either methyl iodide or ethyl chloroformate yielded the unstable ring-opened acetylene derivatives 22a and 22b, respectively. A new synthesis of 1,2-diselenine derivative 33 is reported. Compound 25 formed 1:1 charge-transfer complexes with 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) and with 2,5-dibromo-TCNQ, both of which were electrical insulators. The X-ray crystal structures of compound 25, a charge-transfer complex 25:Br,TCNQ (1:1 stoichiometry) and compound 33 are reported. In the structure of 25:Br,TCNQ, molecules of 25 and Br,TCNQ form mixed stacks. The folding of the donor along the S ... S vector in the complex is 17 degrees (ef. 48 degrees in pure 25) and the conformation of 25 is discussed in the light of previous studies on 1,4-dithiine derivatives. An interesting feature of the crystal structure of 33 is the formation of pseudo-dimers with two short intermolecular Se Se contacts.
• Synthesis of Trithienylenevinylenes Bearing Dithiocarbonate Groups and Their Dithiophene−Tetrathiafulvalene Derivatives
  作者：Xin Chen、Norma R. de Tacconi、Ronald L. Elsenbaumer

  DOI：10.1021/jo901574v

  日期：2009.12.4

  A series of conjugated trithienylenevinylene compounds bearing dithiocarbonate groups were prepared by Wittig reactions. Dithiophene-tetrithiafulvalene (DT-TTF) derivatives can be readily prepared through trialkylphosphite-mediated coupling reactions of these trithienylenevinylene materials. All compounds were characterized by NMR, FT-IR, UV-vis, and mass spectroscopy.