methyl dithio-4-trifluoromethylbenzoate | 5874-10-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl dithio-4-trifluoromethylbenzoate
• 英文别名: p-Trifluormethyl-dithiobenzoesaeure-methylester；Methyl 4-(trifluoromethyl)benzenecarbodithioate；methyl 4-(trifluoromethyl)benzenecarbodithioate
• CAS: 5874-10-2
• 化学式: C₉H₇F₃S₂
• 分子量: 236.282
• InChiKey: GAWINUPCGILWIB-UHFFFAOYSA-N

物化性质

• 沸点：
  98 °C(Press: 0.9 Torr)
• 密度：
  1.340±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  57.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl dithio-4-trifluoromethylbenzoate 、 lithium dimethylcuprate 以 氘代四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Complexes of the Gilman Reagent with Double Bonds across the π–σ Continuum

  摘要：

  By using rapid injection NMR at low temperatures, a variety of pi-complexes of lithium dimethylcuprate(I) with C-C, C-N, and C-S double bonds have been prepared and characterized. Complexation is generally accompanied by large upfield changes in chemical shift for the substrate carbon atoms bonded to copper. In the case of alpha,beta-unsaturated carbonyl compounds, the changes for the carbonyl carbons are much smaller in magnitude, which is consistent with the usual eta(2) representation of these structures. It is possible for one ligand to displace another, and in this way an order of stability can be elucidated. Treatment of selected pi-complexes with chlorosilanes or cyanosilanes gives Cu-III intermediates.

  DOI：

  10.1021/om300622c
• 作为产物：
  描述：

  Sodium; 4-trifluoromethyl-dithiobenzoate 、 硫酸二甲酯 生成 methyl dithio-4-trifluoromethylbenzoate
  参考文献：
  名称：

  Mayer,R. et al., Chemische Berichte, 1966, vol. 99, p. 1393 - 1413

  摘要：

  DOI：

文献信息

• Complexes of Gilman Reagents with C−S and C−N Double Bonds: σ or π Bonding?
  作者：Steven H. Bertz、Yasamin Moazami、Michael D. Murphy、Craig A. Ogle、Joshua D. Richter、Andy A. Thomas

  DOI：10.1021/ja103068h

  日期：2010.7.21

  degrees C inside the probe of an NMR spectrometer to give high yields of complexes. Typical examples of substrates include carbon disulfide, methyl dithioacetate, methyl dithiobenzoate, thiobenzophenone, ethylene trithiocarbonate, and phenyl isothiocyanate. Evidence suggesting the formal oxidation state of copper in these complexes to be Cu(III) is presented. The last example was particularly interesting

  快速注射后，各种硫代羰基化合物与吉尔曼试剂 Me(2)CuLi 在-100 摄氏度的 NMR 光谱仪探头内发生反应，以提供高产率的配合物。底物的典型例子包括二硫化碳、二硫代乙酸甲酯、二硫代苯甲酸甲酯、噻吩二苯甲酮、三硫代碳酸亚乙酯和异硫氰酸苯酯。提供了表明这些配合物中铜的正式氧化态为 Cu(III) 的证据。最后一个例子特别有趣，因为它涉及一个瞬态中间体，该中间体被确定为具有 CN 双键的复合物。异硫氰酸甲酯得到稳定的 CN 双键复合物。
• One-pot synthesis of 2,3-substituted benzo[b]thiophenes via Cu(<scp>i</scp>) catalysed intramolecular cyclisation from dithioesters
  作者：Nagarakere. C. Sandhya、Kebbahalli. N. Nandeesh、Kanchugarakoppal. S. Rangappa、Sannaiah. Ananda

  DOI：10.1039/c5ra02114f

  日期：——

  Efficient synthesis of benzo[b]thiophenes from o-halophenyl acetonitrile has been achieved. This novel one-pot procedure involves CuI and pivalic acid catalyzed C–S bond formation using dithioesters followed by a heterocyclization reaction. This efficient protocol has the advantages of one-pot synthesis, short reaction time, good yields (62–78%) and operational simplicity.

  已从邻卤代苯基乙腈高效合成苯并[ b ]噻吩。这种新颖的一锅法涉及使用二硫代酯和CuI和新戊酸催化的C–S键形成，然后进行杂环化反应。这种高效的方法具有一锅法合成，反应时间短，产率高（62-78％）和操作简便的优点。
• Minimization of Organocuprate Complexity through Self-Organization: Remarkable Orientation Effect in Mixed Cuprate π Complexes
  作者：Steven H. Bertz、Richard A. Hardin、Michael D. Murphy、Craig A. Ogle、Joshua D. Richter、Andy A. Thomas

  DOI：10.1002/anie.201107060

  日期：2012.3.12

  where to go: A powerful orientation effect has been observed in complexes of mixed organocuprates [RTRNTCuLi] and substrates with CC, CN, and CS double bonds (see scheme; Th=thienyl). The preferred geometry of the intermediate complex sets up the facile addition of RT to the double bond, rather than addition of the “dummy ligand”, RNT.

  他们“知道”去哪里：一个强大的取向效应在混合有机铜[R的复合物中观察到Ť ř NT CuLi]和底物使用C  C，C  N，和C  š双键（参见方案; TH =噻吩基）。中间配合物的优选几何形状建立了将R T容易地添加到双键中，而不是添加了“虚拟配体” R NT。
• Mayer,R. et al., Chemische Berichte, 1966, vol. 99, p. 1393 - 1413
  作者：Mayer,R. et al.

  DOI：——

  日期：——
• Complexes of the Gilman Reagent with Double Bonds across the π–σ Continuum
  作者：Steven H. Bertz、Stephen K. Cope、Richard A. Hardin、Michael D. Murphy、Craig A. Ogle、David T. Smith、Andy A. Thomas、Tara N. Whaley

  DOI：10.1021/om300622c

  日期：2012.11.26

  By using rapid injection NMR at low temperatures, a variety of pi-complexes of lithium dimethylcuprate(I) with C-C, C-N, and C-S double bonds have been prepared and characterized. Complexation is generally accompanied by large upfield changes in chemical shift for the substrate carbon atoms bonded to copper. In the case of alpha,beta-unsaturated carbonyl compounds, the changes for the carbonyl carbons are much smaller in magnitude, which is consistent with the usual eta(2) representation of these structures. It is possible for one ligand to displace another, and in this way an order of stability can be elucidated. Treatment of selected pi-complexes with chlorosilanes or cyanosilanes gives Cu-III intermediates.