1,2-双(甲硫基)乙炔 | 59507-56-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫基化合物
• 中文名称: 1,2-双(甲硫基)乙炔
• 英文名称: 1,2-bis(methylthio)acetylene
• 英文别名: bis(methylthio)ethyne；bis(methylthio)acetylene；Bis(methylthio)acetylen；Acetylene, 1,2-dithiomethyl-；1,2-bis(methylsulfanyl)ethyne
• CAS: 59507-56-1
• 化学式: C₄H₆S₂
• mdl: MFCD00241418
• 分子量: 118.224
• InChiKey: KSVSDVXENFYUCT-UHFFFAOYSA-N

物化性质

• 沸点：
  70-75 °C(Press: 14 Torr)
• 密度：
  1.117±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  6
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,2-双(甲硫基)乙炔 在 lithium aluminium tetrahydride 、 copper(I) bromide 作用下， 生成 cis-1,2-bis(mehylthio)ethylene
  参考文献：
  名称：

  Brouwer, A. C.; Bos, H. J. T., Recueil des Travaux Chimiques des Pays-Bas, 1983, vol. 102, # 2, p. 103 - 109

  摘要：

  DOI：
• 作为产物：
  描述：

  2-Methylsulfanyl-3-thioxo-dithioacrylic acid methyl ester 生成 1,2-双(甲硫基)乙炔
  参考文献：
  名称：

  Polycarbon Disulfides SCnS (n = 1-3) and Their Protonated and Methylated Forms (HCnS2+ and CH3CnS2+): Tandem Mass Spectrometry and ab Initio MO Study

  摘要：

  Dissociative ionization of 4,5-bis(methylthio)-1,2-dithiole-3-thione (1) has allowed the detection of a series of carbon disulfide radical cations, SCnS.+ (n = 1-3), and their S-methylated forms, CH3SCnS+, in the gas phase of a mass spectrometer. The connectivities and stabilities of these ions and the corresponding neutrals have been probed by collisional activation (CA) and neutralization-reionization (NR) mass spectrometry. Moreover, the sites of protonation and cationic methylation of the polycarbon disulfides have been investigated by a combination of flash vacuum pyrolysis, chemical ionization, and CAMS (FVP/CI/MS/MS). The experimental results are supported by ab initio MO calculations at the QCISD(T)/6-311+G(2d,p) + ZPVE level. Both experiments and calculations indicate that the most favorable site of protonation and methylation is the carbon atom for C2S2 and C3S2 but a sulfur atom for CS2. The proton affinities (298 K) of C2S2 and C3S2 are predicted to be 842 and 818 kJ mol(-1), respectively.

  DOI：

  10.1021/j100046a010

文献信息

• Pd- and Ni-Catalyzed Cross-Coupling Reactions of Functionalized Organozinc Reagents with Unsaturated Thioethers
  作者：Laurin Melzig、Albrecht Metzger、Paul Knochel

  DOI：10.1002/chem.201002850

  日期：2011.3.1

  serve as electrophiles in this cross‐coupling reaction. Aryl‐, heteroaryl‐, benzylic, and alkylzinc halides with sensitive functionalities, such as ester, nitrile, or ketone groups react at ambient temperature with unsaturated thioethers using a Ni catalyst. The corresponding Pd‐catalyzed reactions require slightly higher temperatures. Large‐scale cross‐coupling experiments (10–20 mmol) with N‐heterocycles

  在过渡金属催化剂的存在下，各种不饱和硫醚与官能化锌试剂进行了交叉偶联反应。基于Pd（OAc）2或[Ni（acac）2的三种不同的催化体系]和配体S-Phos或DPE-Phos给出了最佳结果。基于吡啶，嘧啶，吡嗪，哒嗪，三嗪，苯并噻唑，苯并恶唑，吡咯或喹唑啉环的N-杂环硫醚，以及硫代甲基乙炔，在该交叉偶联反应中用作亲电子试剂。具有敏感官能团（如酯基，腈基或酮基）的芳基，杂芳基，苄基和烷基锌卤化物在室温下使用Ni催化剂与不饱和硫醚反应。相应的Pd催化反应需要稍高的温度。还报道了具有N杂环的大规模交叉偶联实验（10–20 mmol）。
• A Simple and Safe Procedure for Bis(methylthio)- and Bis(ethylthio)acetylene
  作者：H. D. Verkruijsse、L. Brandsma

  DOI：10.1055/s-1991-26578

  日期：——

  The acetylenic derivatives bis(methylthio)- and bis(ethylthio)-acetylene were obtained in high yield by addition of alkyl thiocyanates to solutions of sodium acetylide in liquid ammonia.

  通过将烷基硫氰酸盐加入到乙酰化钠在液氨中的溶液中，可以高产率地获得乙炔衍生物双（甲硫基）-乙炔和双（乙硫基）-乙炔。
• Electrophilic and nucleophilic reactions of complexes formed from 2,5-dithiahex-3-yne (MeSCCSMe) and tungsten carbonyls
  作者：David C. Miller、Robert J. Angelici

  DOI：10.1016/0022-328x(90)87235-6

  日期：1990.8

  MeSCCSMe, reacts with tungsten(II) carbonyl complexes to yield π-alkyne products, CpW(η2-MeSCCSMe)2Cl (1), W(CO)(η2-MeSCCSMe)(S2CNR2)2 (R = Me (2a) and Et (2b)), and W(η2-MeSCCSMe)2(S2CNR2)2 (R = Me (3a) and Et (3b)). The sulfonium complex [CpClW(η2-MeSCCSMe)(η2-MeSCCSMe2)]BF4 (4), whose structure was established by an X-ray diffraction study, was prepared by the reaction of 1 with Me3O+.

  炔，MeSCCSMe，用钨（II）羰基络合物反应，产生π-炔产品，CPW（η 2 -MeSCCSMe）2 Cl（上1），W（CO）（η 2 -MeSCCSMe）（小号2 CNR 2）2（R =我（图2a）和Et（图2b）），并且W（η 2 -MeSCCSMe）2（S 2 CNR 2）2（R =我（图3a）和Et（图3b） ）。锍络合物[CpClW（η 2 -MeSCCSMe）（η 2 -MeSCCSMe 2）] BF 4（4通过1与Me 3 O +的反应制备了通过X射线衍射研究确定其结构的）。
• On the Reaction of<i>N</i>-Arylnitrilium Salts with Acetylenes: Synthesis of Substituted Quinolines
  作者：Mahmoud Al-Talib、Johannes C. Jochims、Quanrui Wang、Atef Hamed、Abd El-Hamid Ismail

  DOI：10.1055/s-1992-26250

  日期：——

  Quinolinium salts 3 are obtained from the reaction of N-arylnitrilium salts 1 with acetylenes 2. With aqueous base the salts 3 are transformed into the corresponding quinolines 4.

  喹啉盐 3 由 N-芳基硝基盐 1 与乙炔 2 反应生成。在水基作用下，盐 3 转化为相应的喹啉 4。
• On the Reaction of<i>N</i>-Alkylnitrilium Salts with Acetylenes: A New Synthesis of 2-Azoniaallene Salts
  作者：Rajab Abu-El-Halawa、Johannes C. Jochims

  DOI：10.1055/s-1992-26249

  日期：——

  N-alkylnitrilium hexachloroantimonates 1 react with phenylacetylene (2a) or bis(methylthio)acetylene (2f) to give 3-azonia-2,3,5-hexatriene hexachloroantimonates 4, which either enolize to furnish 4-alkylidene-2-methyl-6-phenyl-3-azonia-2,4-hexadiene salts 7d,e or cyclize to afford 3,4-bis(methylthio)-2H-pyrrolium salts 6f-k.

  N-烷基硝基六氯锑酸盐 1 与苯乙炔 (2a) 或双(甲硫基)乙炔 (2f) 反应，生成 3-氮杂-2,3,5-己二烯六氯锑酸盐 4，后者或者烯醇化生成 4-亚烷基-2-甲基-6-苯基-3-氮杂-2,4-己二烯盐 7d,e，或者环化生成 3,4-双(甲硫基)-2H-吡咯盐 6f-k。