p-Chlorobenzyl Trifluoromethyl Sulfone | 130774-57-1

• 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: p-Chlorobenzyl Trifluoromethyl Sulfone
• 英文别名: 4-chlorophenylmethyl trifluoromethyl sulfone；1-chloro-4-((trifluoromethylsulfonyl)methyl)benzene；1-Chloro-4-(trifluoromethylsulfonylmethyl)benzene
• CAS: 130774-57-1
• 化学式: C₈H₆ClF₃O₂S
• 分子量: 258.649
• InChiKey: OLTDPBYDRRWVGW-UHFFFAOYSA-N

物化性质

• 熔点：
  95-96 °C
• 沸点：
  322.3±42.0 °C(Predicted)
• 密度：
  1.507±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  p-Chlorobenzyl Trifluoromethyl Sulfone 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 C₁₃H₇ClN₃O₄^(1-)
  参考文献：
  名称：

  4-硝基苯并呋喃与甲醇中苄基三酮衍生的碳负离子反应的动力学研究

  摘要：

  本文报道率测量为负碳离子的从benzyltriflones，衍生反应2，用4- nitrobenzofuroxan，4，在甲醇中，得到阴离子σ-加合物。DMSO- d 6中的1 H NMR研究表明，2和4在三乙胺存在下反应形成的产物与从σ-加成物中消除三氟甲基亚磺酸形成的产物相符，该产物最初是由在室温下通过碳负离子攻击形成的。4的5位。β的低值，它是log k 5对p K a的线性图的斜率提供了对苄基三氟乙烯阴离子的高空间要求的证据。©2012 Wiley Periodicals，Inc.国际化学杂志Kinet 44：546–554，2012

  DOI：

  10.1002/kin.20621
• 作为产物：
  描述：

  p-Chlorobenzyl Trifluoromethanesulfinate 在 2,6-二甲基吡啶 作用下， 以 乙腈 为溶剂， 反应 24.0h， 生成 p-Chlorobenzyl Trifluoromethyl Sulfone
  参考文献：
  名称：

  Braverman, Samuel; Manor, Haim, Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 53, # 1-4, p. 357 - 365

  摘要：

  DOI：

文献信息

• Chemo-, regio- and stereoselective synthesis of monofluoroalkenes <i>via</i> a tandem fluorination–desulfonation sequence
  作者：Ren-Yin Yang、Bo Xu

  DOI：10.1039/d1cc03207k

  日期：——

  approach for the synthesis of Z-monofluoroalkenes from readily available alkyl triflones and NFSI has been reported. The reaction proceeded under mild conditions, affording mono-fluorinated alkenes in good to excellent yields with excellent chemo- regio- and stereoselectivity. The mechanism may involve electrophilic fluorination of triflones followed by the highly stereoselective concerted bimolecular

  已经报道了一种从容易获得的烷基三氟乙烯和 NFSI合成Z-单氟烯烃的广泛适用的方法。该反应在温和的条件下进行，以良好的收率和优异的化学区域选择性和立体选择性提供单氟化烯烃。该机制可能涉及三氟酮的亲电氟化，然后是 CF 3 SO 2 H的高度立体选择性协同双分子消除 (E2) 。
• Catalytic and Highly Enantioselective Reactions of α-Sulfonyl Carbanions with Chiral Bis(oxazoline)s
  作者：Shuichi Nakamura、Norimune Hirata、Ryusuke Yamada、Takeshi Kita、Norio Shibata、Takeshi Toru

  DOI：10.1002/chem.200800221

  日期：2008.6.20

  The enantioselective reactions of lithiated benzyl trifluoromethyl sulfones with a substoichiometric amount of a bis(oxazoline) and various aldehydes is disclosed. The products were formed with excellent diastereo- and enantioselectivities. Fluorination of the sulfone with N-fluorobenzenesulfonimide and a stoichiometric amount of a bis(oxazoline) gave products with extremely high enantioselectivities

  公开了锂化的苄基三氟甲基砜与亚化学计量的双（恶唑啉）和各种醛的对映选择性反应。形成的产物具有优异的非对映选择性和对映选择性。用N-氟苯磺酰亚胺和化学计量的双（恶唑啉）对砜进行氟化，得到的产物具有极高的对映选择性（高达99％ee； ee =对映体过量）。确认对映选择性反应通过动态热力学拆分途径进行。
• Gas-Phase Acidities of α- and α,α-SO₂CF₃-Substituted Toluenes. Varying Resonance Demand in the Electron-Rich System
  作者：Min Zhang、Md. Mizanur Rahman Badal、Ilmar A. Koppel、Masaaki Mishima

  DOI：10.1246/bcsj.20130052

  日期：2013.7.15

  The gas-phase acidities (GA) of aryl(trifluoromethylsulfonyl)methanes (ArCH2SO2CF3; 1) and arylbis(trifluoromethylsulfonyl)methanes (ArCH(SO2CF3)2; 2) were determined by measuring proton-transfer equilibria. Substituent effects for acidities of a series of ArCH(R1)R2 including 1 and 2 have been analyzed successfully in terms of the Yukawa–Tsuno equation. The resonance demand parameter r− value was found to decrease linearly with increasing acidity of the GA values of the unsubstituted parent carbon acids, and the change of the r− value was correlated with the acidifying effect of the phenyl group (R = Ph) in the RCH2(R1)R2. In addition, the geometric features and natural charges of the conjugate anions calculated at B3LYP/6-311+G(d,p) were found to be correlated linearly with the r− values. Such behavior of the resonance demand parameter in the electron-rich system, ArC−(R1)R2, is completely consistent with that observed for the electron-deficient system, ArC+(R1)R2, revealing that the resonance demand is contingent upon the structure of carbanions and carbocations. Furthermore, it was found that the ρ values also decreased with increasing acidity of the GA values of the unsubstituted parent carbon acids. This would be related to the distribution of the charge between the aromatic moiety and the C(R1)R2 moiety.

  通过测量质子转移平衡，确定了芳基(三氟甲基磺酰基)甲烷（ArCH2SO2CF3；1）和芳基双(三氟甲基磺酰基)甲烷（ArCH(SO2CF3)2；2）的气相酸度（GA）。根据 Yukawa-Tsuno 方程，成功地分析了包括 1 和 2 在内的一系列 ArCH(R1)R2 酸性的取代基效应。研究发现，共振需求参数 r- 值随着未取代母体碳酸的 GA 值的酸度增加而线性降低，r- 值的变化与 RCH2(R1)R2 中苯基（R = Ph）的酸化效应相关。此外，B3LYP/6-311+G(d,p)计算得出的共轭阴离子的几何特征和自然电荷与 r- 值呈线性相关。在富电子体系 ArC-(R1)R2 中，共振需求参数的这种行为与在缺电子体系 ArC+(R1)R2 中观察到的行为完全一致，揭示了共振需求取决于碳离子和碳阳离子的结构。此外，研究还发现，随着未取代母体碳酸 GA 值酸度的增加，ρ 值也会降低。这与芳香族分子和 C(R1)R2 分子之间的电荷分布有关。
• Copper-Catalyzed Direct Trifluoromethylthiolation of Benzylic C–H Bonds via Nondirected Oxidative C(sp³)–H Activation
  作者：Chao Chen、Xiu-Hua Xu、Bin Yang、Feng-Ling Qing

  DOI：10.1021/ol501400u

  日期：2014.6.20

  A copper-catalyzed trifluoromethylthiolation of benzylic sp(3) C-H bonds was developed via nondirected oxidative C-H activation using readily prepared and stable AgSCF3. This reaction provides a novel and straightforward method for the preparation of various benzyl trifluoromethyl sulfides.
• BRAVERMAN, SAMUEL;MANOR, HAIM, PHOSPH., SULFUR AND SILICON AND RELAT. ELEM., 53,(1990) N-4, C. 357-365
  作者：BRAVERMAN, SAMUEL、MANOR, HAIM

  DOI：——

  日期：——