1-(4-chlorophenyl)-2,2-difluoro-2-(phenylsulfonyl)ethan-1-ol | 122590-89-0

• 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: 1-(4-chlorophenyl)-2,2-difluoro-2-(phenylsulfonyl)ethan-1-ol
• 英文别名: 1-(4-chlorophenyl)-2,2-difluoro-2-(phenylsulfonyl)ethanol；4-chloro-[difluoro(phenylsulfony)methyl]-benzenemethanol；1-(4-chlorophenyl)-2,2-difluoro-2-phenylsulfonylethanol；1-(4-Chlorophenyl)-2.2-difluoro-2-phenylsulfonylethanol；alpha-(Phenylsulfonyldifluoromethyl)-4-chlorobenzenemethanol；2-(benzenesulfonyl)-1-(4-chlorophenyl)-2,2-difluoroethanol
• CAS: 122590-89-0
• 化学式: C₁₄H₁₁ClF₂O₃S
• 分子量: 332.755
• InChiKey: AFIDLWGRUFLIDL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  62.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-(4-chlorophenyl)-2,2-difluoro-2-(phenylsulfonyl)ethan-1-ol 在 sodium acetate 、 magnesium 、 溶剂黄146 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 以83%的产率得到1-(4-chlorophenyl)-2,2-difluoroethan-1-ol
  参考文献：
  名称：

  Nucleophilic difluoromethylation of carbonyl compounds using TMSCF2SO2Ph and Mg0-mediated desulfonylation

  摘要：

  A new nucleophilic difluoromethylation chemistry using fluoride-induced (phenylsulfonyl)difluoromethylation with TMSCF2SO2Ph followed by the magnesium-metal-mediated desulfonylation has been achieved. This methodology is compatible with both enolizable and non-enolizable aldehydes and ketones and has special advantage in the case of enolizable aldehydes. The new efficient desulfonylation method is considered to be environmentally benign due to the absence of mercury. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.09.162
• 作为产物：
  描述：

  ethyl 2,2-difluoro-2-(phenylthio)acetate 在 sodium periodate 、 ruthenium(III) trichloride hydrate 、 potassium hydroxide 作用下， 以 甲醇 、 四氯化碳 、 水 、 乙腈 为溶剂， 反应 49.0h， 生成 1-(4-chlorophenyl)-2,2-difluoro-2-(phenylsulfonyl)ethan-1-ol
  参考文献：
  名称：

  醛和亚胺的脱羧亲核二氟甲基化

  摘要：

  对具有生物活性的CF 2 H分子的高需求刺激了巨大的努力，以开发用于安装CF 2 H官能团的有效方法。我们发现，苯基磺酰基二氟乙酸盐（PhSO 2 CF 2 CO 2 - ķ +）可直接经受在温热条件下产生活性阴离子（PhSO脱羧2 CF 2 - ），而不需要任何碱或添加剂的，因此允许随后的亲核醛或亚胺的（苯磺酰基）二氟甲基化，生成PhSO 2 CF 2-醇或-胺。有趣的是，仅通过升高用于转化醛以提供CF 2 H-酮的反应温度即可实现PhSO 2基团的去除。

  DOI：

  10.1016/j.tet.2018.06.062

文献信息

• Process for nucleophilic fluoroalkylation of aldehydes
  申请人：Ethyl Corporation

  公开号：US04837327A1

  公开（公告）日：1989-06-06

  Aryl difluoromethyl sulfone adds to alkehydes under phase transfer conditions to give novel substituted alcohols of the general formula RCH(OH)CF.sub.2 SO.sub.2 Ar (I) wherein R is an aryl, cycloaliphatic, sec- or tert-aliphatic, or heterocyclic group and Ar is an aryl group. The substituted alcohols of formula I are of particular utility as intermediates in the synthesis of a variety of useful end products. For example, the products of formula I may be utilized in desulfonylation reactions, oxidation reactions and fluorination reactions.

  芳基二氟甲基砜在相转移条件下与醛反应，生成一般式为RCH(OH)CF.sub.2 SO.sub.2 Ar（I）的新型取代醇，其中R为芳基、环脂肪、次级或三级脂肪或杂环基团，Ar为芳基。式I的取代醇在合成各种有用终产物的中间体方面具有特殊的实用性。例如，式I的产物可用于脱砜反应、氧化反应和氟化反应。
• Nucleophilic (Phenylsulfonyl/arylthio)difluoromethylation of Aldehydes with TMSCF₂Br: A Three-Component Strategy
  作者：Qiqiang Xie、Ziyue Zhu、Chuanfa Ni、Jinbo Hu

  DOI：10.1021/acs.orglett.9b03520

  日期：2019.11.15

  (phenylsulfonyl/arylthio)difluoromethylation of aldehydes with TMSCF2Br was developed. The reaction proceeds through in situ generation of difluorocarbene, which is captured by PhSO2Na or ArSNa to form the corresponding PhSO2CF2- or PhSCF2- anions, followed by nucleophilic addition to aldehydes to give the desired difluoromethylated products.

  建立了一种用TMSCF2Br进行醛类亲核（苯磺酰基/芳硫基）二氟甲基化的有效方法。该反应通过原位产生二氟卡宾而进行，该二氟卡宾被PhSO 2 Na或ArSNa捕获以形成相应的PhSO 2 CF 2-或PhSCF 2-阴离子，然后亲核加成至醛中以得到所需的二氟甲基化产物。
• Nucleophilic addition of difluoromethyl phenyl sulfone to aldehydes and various transformations of the resulting alcohols
  作者：G.Patrick Stahly

  DOI：10.1016/s0022-1139(00)81636-x

  日期：1989.4

  Nucleophilic addition of difluoromethyl phenyl sulfone (1) to various aldehydes occurred in a two phase system (50% aqueous sodium hydroxide, dichloromethane. Aliquat® 336) to give difluoro(phenylsulfonyl)methyl substituted alcohols (2/28). The product alcohol derived from para-tolualdehyde was converted to the difluoromethylated alcohol by desulfonylation and to the α, β, β-trifluorostyrene by a

  在两相系统（50％氢氧化钠水溶液，二氯甲烷，Aliquat®336）中，将二氟甲基苯砜（1）亲核加成，得到二氟（苯磺酰基）甲基取代的醇（2/28）。衍生自对甲苯甲醛的产物醇通过去磺酰化被转化为二氟甲基化的醇，并且通过氟化消除序列被转化为α，β，β-三氟苯乙烯。在没有醛的情况下，1在两相体系中反应生成二氟（苯磺酰基）甲基苯硫醚（9）。研究了后者转化的途径。
• Decarboxylative difluoromethylation of aldehydes with PhSO 2 CF 2 COOK: A facile and efficient access to difluoromethylated carbinols
  作者：Yu-Jun Zhu、Zhong-Liang Lei、Da-Kang Huang、Bo Lian、Zhen-Jiang Liu、Xiao-Jun Hu、Jin-Tao Liu

  DOI：10.1016/j.tetlet.2018.07.021

  日期：2018.8

  A novel decarboxylative difluoromethylation reaction of PhSO2CF2COOK with aldehydes under metal- and ligand-free conditions has been developed. The reaction is very mild and tolerates a wide range of aldehydes (both enolizable and non-enolizable aldehydes), providing a facile and efficient method for the synthesis of structurally diverse difluoromethylated carbinols in moderate to excellent yields

  在无金属和无配体条件下，开发了PhSO 2 CF 2 COOK与醛类的新型脱羧二氟甲基化反应。该反应非常温和，并且可以耐受多种醛类（可烯醇化和不可烯醇化的醛），为合成结构多样的二氟甲基化甲醇提供了简便而有效的方法，产率中等至优异。
• Efficient nucleophilic difluoromethylation of aldehydes with (phenylsulfonyl)difluoromethylzinc and (phenylsulfonyl)difluoromethylcadmium reagents
  作者：Fanzhou Jiang、Chuanfa Ni、Jinbo Hu

  DOI：10.1016/j.jfluchem.2016.12.005

  日期：2017.6

  strategy for nucleophilic addition to aldehydes with difluoromethyl organometallic reagents has been developed by functionalizing the difluoromethyl moiety with the phenylsulfonyl group (SO2Ph). This electron-withdrawing group influences both the thermodynamic stability and the nucleophilicity of difluoromethyl organometallic reagents, which plays an important role in the nucleophilic difluoromethylation

  通过用苯磺酰基（SO 2 Ph）官能化二氟甲基部分，已经开发了一种用二氟甲基有机金属试剂亲核加成醛的新策略。该吸电子基团影响二氟甲基有机金属试剂的热力学稳定性和亲核性，这在醛的亲核二氟甲基化中起重要作用。