2,3-bis(methylthio)tetrathiafulvalene | 118148-28-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二硫醇
• 英文名称: 2,3-bis(methylthio)tetrathiafulvalene
• 英文别名: 4,5-bis(methylthio)tetrathiafulvalene；1,3-Dithiole, 2-(1,3-dithiol-2-ylidene)-4,5-bis(methylthio)-；2-(1,3-dithiol-2-ylidene)-4,5-bis(methylsulfanyl)-1,3-dithiole
• CAS: 118148-28-0
• 化学式: C₈H₈S₆
• 分子量: 296.548
• InChiKey: QNHKZXOAIWVKMV-UHFFFAOYSA-N

物化性质

• 沸点：
  319.4±42.0 °C(Predicted)
• 密度：
  1.58±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  152
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3-bis(methylthio)tetrathiafulvalene 在 正丁基锂 、 bis(phenylethynyl)telluride 作用下， 生成 5,11-Bis[4,5-bis(methylsulfanyl)-1,3-dithiol-2-ylidene]-4,6,10,12-tetrathia-2,8-ditelluratricyclo[7.3.0.03,7]dodeca-1(9),3(7)-diene
  参考文献：
  名称：

  独特的分子供体，包含两个与1,4-二硬脂灵融合的四硫富富瓦烯（TTF）单元：合成，X射线结构和循环伏安法

  摘要：

  合成了一种新的分子供体，该分子由两个与1，4-二tellururin（3）融合的TTF部分组成，并通过X射线衍射对其结构进行了表征。3及其甲基类似物4的循环伏安法显示两个可逆的两电子氧化波。

  DOI：

  10.1016/s0040-4039(00)74440-6
• 作为产物：
  描述：

  四硫富瓦烯 在 正丁基锂 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 15.58h， 生成 2,3-bis(methylthio)tetrathiafulvalene
  参考文献：
  名称：

  TIPS-TTF为低对称性TTF衍生物的前体：位阻保护战略的区域选择性Ç ？H修改TTF

  摘要：

  三异丙基甲硅烷基四硫富瓦烯（TIPS-TTF）被设计为合成低对称TTF衍生物的有前途的平台。庞大的TIPS组允许TIPS‐TTF仅在更宽敞的二硫环上进行钯催化的直接二芳基化以及LDA介导的二氢键化。随后的氟化物介导的protodesilylation提供了病毒双功能化的TTF，可以进一步进行功能化。

  DOI：

  10.1002/chem.201300623

文献信息

• Chiroptical properties of 1,3-diphenylallene-anchored tetrathiafulvalene and its polymer synthesis
  作者：Masashi Hasegawa、Junta Endo、Seiya Iwata、Toshiaki Shimasaki、Yasuhiro Mazaki

  DOI：10.3762/bjoc.11.109

  日期：——

  prepared as an optically active compound having strong chiroptical properties. Although a chiral allene bearing strong electron-donating group(s) often undergoes slow photoracemization even in daylight, the present allene is totally configurationally stable under ordinary conditions. Each isomer possesses pronounced chiroptical properties in its ECD spectra reflecting the chiral allene framework. Moreover

  已经制备了通过手性1，3-二苯基亚烷基骨架桥接的新型四硫富瓦烯二聚体，作为具有强手性的光学活性化合物。尽管带有强电子给体基团的手性异戊二烯即使在白天也经常经历缓慢的光消旋作用，但本发明的异戊二烯在普通条件下是完全构型稳定的。每种异构体在其ECD光谱中均具有明显的手性，反映了手性异戊烯骨架。此外，还通过TTF单元的直接CH活化来进行手性主链的延长，并且还研究了所得聚合物的手性。
• 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。
• Face-to-Face Dimeric Tetrathiafulvalenes and Their Cation Radical and Dication Species as Models of Mixed Valence and π-Dimer States
  作者：Masashi Hasegawa、Kota Daigoku、Kenro Hashimoto、Hiroyuki Nishikawa、Masahiko Iyoda

  DOI：10.1246/bcsj.20110224

  日期：2012.1.15

  Intramolecular interactions of face-to-face tetrathiafulvalenes (TTFs) in 1,8-bis(tetrathiafulvalenyl)naphthalene frameworks were investigated in neutral and cationic states. From X-ray analysis an...

  在中性和阳离子状态下研究了 1,8-双（四硫富瓦烯基）萘骨架中面对面四硫富瓦烯 (TTF) 的分子内相互作用。从 X 射线分析和...
• Redox-active tetrathiafulvalene and dithiolene compounds derived from allylic 1,4-diol rearrangement products of disubstituted 1,3-dithiole derivatives
  作者：Filipe Vilela、Peter J Skabara、Christopher R Mason、Thomas D J Westgate、Asun Luquin、Simon J Coles、Michael B Hursthouse

  DOI：10.3762/bjoc.6.113

  日期：——

  We present a series of compounds by exploiting the unusual 1,4-aryl shift observed for electron-rich 1,3-dithiole-2-thione and tetrathiafulvalene (TTF) derivatives in the presence of perchloric acid. The mechanistic features of this rearrangement are discussed since this synthetic strategy provides an alternative route for the synthesis and functionalisation of sulfur rich compounds including redox active compounds of TTFs, and a Ni dithiolene.

  我们通过利用在高氯酸存在下观察到的富电子1,3-二硫代二唐和四硫富瓦烯（TTF）衍生物的不寻常的1,4-芳基转移，提出了一系列化合物。讨论了这种重排的机制特征，因为这种合成策略为合成和功能化硫富化合物提供了一条替代途径，包括TTF的氧化还原活性化合物和Ni二硫代烯。
• 2,5-Bis(1′,3′-dithiol-2′-ylidene)-1,3,4,6-tetrathiapentalene and Its Related Unsymmetrical Donors
  作者：Yohji Misaki、Toshitaka Matsui、Kazuya Kawakami、Hiroyuki Nishikawa、Tokio Yamabe、Motoo Shiro

  DOI：10.1246/cl.1993.1337

  日期：1993.8

  The title compound (1a) and its related unsymmetrical derivatives were prepared as new donors for organic conductors, and electrochemical properties and crystal structure of 1a were investigated. Several charge-transfer complexes and cation radical salts using them showed metallic temperature dependence of conductivity down to ca. 100 K.

  制备了标题化合物(1a)及其相关的不对称衍生物作为有机导体的新供体，并研究了1a的电化学性质和晶体结构。使用它们的几种电荷转移复合物和阳离子自由基盐显示出金属温度依赖性的电导率低至约 。100K。