4,5-dibromo-1,3-dithiole-2-thione | 209334-74-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: 4,5-dibromo-1,3-dithiole-2-thione
• CAS: 209334-74-7
• 化学式: C₃Br₂S₃
• 分子量: 292.039
• InChiKey: OWFANQJGQIYARQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  8
• 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：
  82.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4,5-dibromo-1,3-dithiole-2-thione 在 mercury(II) diacetate 、 溶剂黄146 作用下， 以 氯仿 为溶剂， 反应 2.0h， 以65%的产率得到4,5-dibromo-1,3-dithiole-2-one
  参考文献：
  名称：

  Hal⋯Hal interactions in a series of three isostructural salts of halogenated tetrathiafulvalenes. Contribution of the halogen atoms to the HOMO–HOMO overlap interactions

  摘要：

  卤化的四硫富瓦烯 Br2-EDT-TTF 和 I2-EDT-TTF 通过相应的 4,5-二溴或 4,5-二碘-1,3-二硫醇-2-酮的偶联途径制备。在同构系列中，(Br2-EDT-TTF)2IBr2、(Br2-EDT-TTF)2I3 和 (I2-EDT-TTF)2I3，分别记为 Br2/IBr2、Br2/I3 和 I2/I3，鉴定出短程（3.42–3.60 Å）且定向的卤-卤相互作用存在于供体分子与阴离子之间，从而稳定了稀有的 β′ 相。这些相互作用不仅发挥结构作用，还通过 Br2-EDT-TTF 和 I2-EDT-TTF 中 HOMOs 上卤素原子的显著系数对电子分散产生贡献。这三种盐表现出莫特绝缘体特性，其高室温电导率（0.5 S cm⁻¹）反映出其活化能按 Br2/IBr2 (730 K)、Br2/I3 (1260 K) 和 I2/I3 (1330 K) 的顺序增加，且具有较弱的磁化率，在 150 K 以下急剧下降，未出现反铁磁基态的迹象。

  DOI：

  10.1039/b100103p
• 作为产物：
  描述：

  三硫代碳酸亚乙烯酯 在 lithium diisopropyl amide 、 1,2-二溴四氯乙烷 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以52%的产率得到4,5-dibromo-1,3-dithiole-2-thione
  参考文献：
  名称：

  Hal⋯Hal interactions in a series of three isostructural salts of halogenated tetrathiafulvalenes. Contribution of the halogen atoms to the HOMO–HOMO overlap interactions

  摘要：

  卤化的四硫富瓦烯 Br2-EDT-TTF 和 I2-EDT-TTF 通过相应的 4,5-二溴或 4,5-二碘-1,3-二硫醇-2-酮的偶联途径制备。在同构系列中，(Br2-EDT-TTF)2IBr2、(Br2-EDT-TTF)2I3 和 (I2-EDT-TTF)2I3，分别记为 Br2/IBr2、Br2/I3 和 I2/I3，鉴定出短程（3.42–3.60 Å）且定向的卤-卤相互作用存在于供体分子与阴离子之间，从而稳定了稀有的 β′ 相。这些相互作用不仅发挥结构作用，还通过 Br2-EDT-TTF 和 I2-EDT-TTF 中 HOMOs 上卤素原子的显著系数对电子分散产生贡献。这三种盐表现出莫特绝缘体特性，其高室温电导率（0.5 S cm⁻¹）反映出其活化能按 Br2/IBr2 (730 K)、Br2/I3 (1260 K) 和 I2/I3 (1330 K) 的顺序增加，且具有较弱的磁化率，在 150 K 以下急剧下降，未出现反铁磁基态的迹象。

  DOI：

  10.1039/b100103p

文献信息

• Selective Metalation of 1,3-Dithiole-2-thiones: An Effective Preparation of New Symmetrically and Nonsymmetrically Tetraarylated Tetrathiafulvalenes
  作者：Paul Knochel、Julia Nafe

  DOI：10.1055/s-0035-1560728

  日期：——

  tetrathiafulvalenes of interest as organic materials. We report an efficient preparation of fully functionalized tetrathiafulvalene derivatives (TTF) with an extended π-system via a selective magnesiation of 1,3-dithiole-2-thiones (DTT) using 2,2,6,6-tetramethylpiperidin-1-ylmagnesium chloride–lithium chloride (TMPMgCl·LiCl); subsequent reaction with various electrophiles, such as halides, acid chlorides, allyl

  摘要 我们报告通过使用2,2,6,6-四甲基哌啶-1-基镁对1,3-二硫代-2-硫酮（DTT）的选择性放大作用，有效制备具有扩展的π系统的全功能化四硫富瓦烯衍生物（TTF）氯化物-氯化锂（TMPMgCl·LiCl）；随后与各种亲电子试剂（如卤化物，酰氯，烯丙基溴和芳基碘化物）的反应顺利地产生了新的单官能和双官能化的1,3-二硫代-2-硫酮衍生物。亚磷酸三乙酯介导的二取代的1，3-二硫代-2-硫酮衍生物与它们的氧类似物的交叉偶合，使人们有兴趣获得新的对称和不对称的四芳基四硫富瓦烯作为有机材料。 我们报告通过使用2,2,6,6-四甲基哌啶-1-基镁对1,3-二硫代-2-硫酮（DTT）的选择性放大作用，有效制备具有扩展的π系统的全功能化四硫富瓦烯衍生物（TTF）氯化物-氯化锂（TMPMgCl·LiCl）；随后与各种亲电子试剂（如卤化物，酰氯，烯丙基溴和芳基碘化物）的反应顺利地产生了新的单官能和双官能化的1
• Synthesis and crystal engineering of new halogenated tetrathiafulvalene (TTF) derivatives and their charge transfer complexes and radical ion salts
  作者：Andrei S. Batsanov、Martin R. Bryce、Antony Chesney、Judith A. K. Howard、Derek E. John、Adrian J. Moore、Clare L. Wood、Hagit Gershtenman、James Y. Becker、Vladimir Y. Khodorkovsky、Arkady Ellern、Joel Bernstein、Igor F. Perepichka、Vincent Rotello、Mark Gray、Alejandro O. Cuello

  DOI：10.1039/b101866n

  日期：——

  Efficient syntheses are reported for tetraiodotetrathiafulvalene 2, 4-iodo-5-methyl-4′,5′-bis(methylsulfanyl)TTF 3, and 4-iodo-4′,5′-bis(methylsulfanyl)TTF 4 by iodination, using perfluorohexyl iodide, of lithiated derivatives of the corresponding TTF system. Bromination and chlorination of lithiotrimethylTTF using 1,2-dibromotetrafluoroethane and hexachloroethane gave 4-bromo- and 4-chloro-4′,5,5′-trimethylTTF 6 and 7, respectively. Phosphite-induced self-coupling or cross-coupling reactions of 4-iodo-1,3-dithiole-2-thione or 4,5-diiodo-1,3-dithiole-2-thione(one) half-units resulted in TTF derivatives with partial loss of the iodine substituent(s). 4,5-Dibromo-4′,5′-bis(cyanoethylsulfanyl)TTF 15 was prepared by cross-coupling methodology, and converted into 4,5-dibromo-4′,5′-bis(methylsulfanyl)TTF 16 by reaction with caesium hydroxide and then methyl iodide. EPR data are reported for the electrochemically generated cation radicals of trimethylTTFX derivatives (X = I, Br and Cl) 5–7, respectively. For the neutral donors, the X-ray crystal structures are reported for 2, 5, 6, tetramethylTTF 8 and 15. Structure 2 is characterised by a particularly dense packing with continuous chains of intra-stack I⋯I contacts (4.17–4.19 Å). The crystals of 6 and 8 are isomorphous, while the structure of 5 is different. The iodo-substituent in 5 affects the packing in a way the bromo-substituent in 6 does not, due to differences in specific interactions rather than steric demands of I and Br, which are similar. Structure 15 comprises face-to-face dimers with inter-dimer Br⋯Br (3.57 Å) and Br⋯S (3.55 Å) contacts: a remarkable difference in bond distances between the Br and S-substituted dithiole rings is observed. The 1 ∶ 1 charge-transfer (CT) complexes 3·TCNQ and 4·TCNQ (TCNQ = 7,7,8,8-tetracyano-p-quinodimethane, 17) display mixed stair-like stacks of alternating D and A moieties: the overall degree of CT is estimated from bond length analysis to be 0.2 e and 0.3 e, respectively. In 3·TCNQ either position of the disordered iodine atom has one short (inter-stack, but intra-layer) contact with a cyano group (I⋯N distances of 3.14 and 3.18 Å). In 4·TCNQ a similar I⋯N contact is much longer (3.35 Å). In the structure of 5+·I3−·½I2 the cation radical is disordered; dimeric cation radicals display short intra-dimer contacts (S⋯S 3.38–3.39 Å, C⋯C 3.35 Å) consistent with electron coupling. Each dimer is surrounded by four I3− anions. The crystal structure of 16+·I3− is comprised of layers with interplanar separations of 3.55 Å. Cations of one layer overlap with anions of the next, and the packing can be described as mixed stacks parallel to the a axis. The remarkably high conductivity of this salt for a system of 1 ∶ 1 stoichiometry (σrt = 8 × 10−2 S cm−1) is ascribed to partial charge transfer (the charge on the TTF moiety is estimated as +⅔ from bond length analysis) and a continuous system of short non-bonding contacts.

  报道了四碘四硫富瓦烯的高效合成方法，4-碘-5-甲基-4′,5′-双(甲基硫巴)TTF 3，以及4-碘-4′,5′-双(甲基硫巴)TTF 4，该方法通过用全氟己基碘对相应TTF体系的锂化衍生物进行碘化反应。使用1,2-二溴四氟乙烷和六氯乙烷对锂三甲基TTF进行溴化和氯化，分别得到了4-溴-和4-氯-4′,5,5′-三甲基TTF 6和7。由磷酸酯诱导的4-碘-1,3-二噁烯-2-硫酮或4,5-二碘-1,3-二噁烯-2-硫酮(一个)半单元的自偶联或交叉偶联反应导致TTF衍生物伴有部分碘取代基的损失。通过交叉偶联方法合成了4,5-二溴-4′,5′-双(氰乙基硫巴)TTF 15，并通过与氢氧化铯和随后与碘甲烷的反应转化为4,5-二溴-4′,5′-双(甲基硫巴)TTF 16。报告了为电化学生成的三甲基TTF衍生物(X = I, Br和Cl)的阳离子自由基进行的电子顺磁共振(EPR)数据。对于中性给体，报告了2、5、6、四甲基TTF 8和15的X射线晶体结构。结构2的特征在于具有特别密集的堆积形态，形成连续的堆叠内I⋯I接触(4.17–4.19 Å)。6和8的晶体是同构的，而5的结构则不同。由于特定相互作用的差异，而不是I和Br相似的立体要求，使得5中的碘取代基影响了堆积，而6中的溴取代基则没有。结构15由面对面二聚体组成，具有二聚体间的Br⋯Br(3.57 Å)和Br⋯S(3.55 Å)接触：观察到Br和S取代的二噁烯环之间的键长距离存在显著差异。1:1电荷转移(CT)复合物3·TCNQ和4·TCNQ(TCNQ = 7,7,8,8-四氰基-p-奎诺二甲烷，17)显示出交替的D和A基团的混合阶梯状堆叠：通过键长分析估计的CT整体程度分别为0.2 e和0.3 e。在3·TCNQ中，无序的碘原子在某个位置与一个氰基之间有一个短的(堆叠间，但层内)接触(I⋯N距离为3.14和3.18 Å)。在4·TCNQ中，类似的I⋯N接触则较长(3.35 Å)。在结构5+·I3−·½I2中，阳离子自由基无序；二聚阳离子自由基显示短的二聚内接触(S⋯S 3.38–3.39 Å, C⋯C 3.35 Å)，与电子耦合一致。每个二聚体周围都有四个I3−阴离子。16+·I3−的晶体结构由层组成，层间距离为3.55 Å。一个层的阳离子与下一个层的阴离子重叠，堆积可描述为沿a轴的混合堆叠。这种1:1化学计量比体系的盐具有显著高的导电性(σrt = 8 × 10−2 S cm−1)，归因于部分电荷转移(通过键长分析估计TTF基团的电荷为+⅔)和一种连续的短非键接触体系。
• Efficient synthesis of brominated tetrathiafulvalene (TTF) derivatives: solid-state structure and electrochemical behaviour
  作者：Antonio Alberola、Rebecca J. Collis、Felipe García、Ruth E. Howard

  DOI：10.1016/j.tet.2006.06.006

  日期：2006.8

  An efficient synthesis is reported for 4,5-dibromo-[1,3]dithiole-2-thione (1) and 4-bromo-1,3-dithiole-2-thione (7) by bromination of lithiated vinylene trithiocarbonate. Compound 1 acts as a convenient precursor to a number of asymmetric electron donors. This is exemplified by the formation of 4,5-dibromo-4′,5′-bis(2′-cyanoethylsulfanyl)TTF (3) by cross-coupling methodology and subsequent conversion

  据报道，通过溴化锂化的亚乙烯基三硫代碳酸酯可以有效合成4,5-二溴-[1,3]二硫代-2-硫酮（1）和4-溴-1,3-二硫代-2-硫酮（7）。化合物1充当许多不对称电子供体的便利前体。这通过交叉偶联方法形成4,5-二溴-4'，5'-双（2'-氰基乙基硫基）TTF（3）并随后转化为4,5-二溴-4'，5'来举例说明-乙烯二硫代TTF（4）通过与氢氧化铯和1，2-二溴乙烷反应。新的供体4,5-二溴4'，5'-亚乙基二硫代二硒二氮富瓦烯（5）是通过将1和4,5-亚乙基二硫-1,3-二硒酚-2-一（6）。报告了3和5的X射线结构。
• Syntheses, Structure and Conducting Properties of Halogenated Ethylenedioxytetrathiafulvalenes
  作者：Masahiko Iyoda、Yoshiyuki Kuwatani、Eiji Ogura、Kenji Hara、Hironori Suzuki、Takahiro Takano、Koji Takeda、Jun-ichi Takano、Kohei Ugawa、Masato Yoshida、Haruo Matsuyama、Hiroyuki Nishikawa、Isao Ikemoto、Takehiro Kato、Naoki Yoneyama、Jun-ichi Nishijo、Akira Miyazaki、Toshiaki Enoki

  DOI：10.3987/com-00-s(i)79

  日期：——

  4,5-Diiodo-, 4,5-dibromo-, and 4,5-dichloro-4',5'-ethylenedioxytetra-thiafulvalenes (EDO-TTFI2, EDO-TTFBr2, and EDO-TTFCl2) were synthesized in moderate to good yields by the two routes. The first route contains the reaction of EDO-TTF with LDA, followed by quenching with halogenated reagents, and the second route consists of the P(OR)(3)-mediated cross-coupling of 4,5-dihalogenated 1,3-dithiole-2-ones with 4,5-ethylenedioxy-1,3-dithiole-2-thione. The structures of EDO-TTFI2 and EDO-TTFCl2 were determined by X-Ray analysis. The radical-cation salts derived from EDO-TTFI2, EDO-TTFBr2, and EDO-TTFCl2 show high conductivities, although these compounds contain electron-withdrawing halogens as the substituent.