4-bromo-[difluoro(phenylsulfony)methyl]-benzenemethanol | 895164-05-3

• 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: 4-bromo-[difluoro(phenylsulfony)methyl]-benzenemethanol
• 英文别名: 1-(4-bromophenyl)-2,2-difluoro-2-(phenylsulfonyl)ethanol；1-(4-bromophenyl)-2,2-difluoro-2-(phenylsulfonyl)ethan-1-ol；2-(Benzenesulfonyl)-1-(4-bromophenyl)-2,2-difluoroethanol
• CAS: 895164-05-3
• 化学式: C₁₄H₁₁BrF₂O₃S
• 分子量: 377.206
• InChiKey: AMCRVGZRVPLKBO-UHFFFAOYSA-N

物化性质

• 沸点：
  537.7±50.0 °C(Predicted)
• 密度：
  1.613±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 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：

  4-bromo-[difluoro(phenylsulfony)methyl]-benzenemethanol 在 4-二甲氨基吡啶 、 disodium hydrogenphosphate 、 sodium amalgam 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 4-溴-β,β-二氟苯乙烯
  参考文献：
  名称：

  亲核性二氟甲基化和使用溴二氟甲基苯基砜的二氟甲基化

  摘要：

  已发现四（二甲基氨基）乙烯（TDAE）是一种有效的电子转移剂，可促进溴二氟甲基苯基砜与醛的反应，从而以高收率获得结构多样的（苯磺酰基）二氟甲基化醇，可将其进一步转化为二氟甲基醇和1,1-二氟-1-烯烃分别通过还原性脱磺酰基反应和朱莉娅烯化反应。

  DOI：

  10.1016/j.jfluchem.2005.07.011
• 作为产物：
  描述：

  在 四丁基氟化铵 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 生成 4-bromo-[difluoro(phenylsulfony)methyl]-benzenemethanol
  参考文献：
  名称：

  Nucleophilic difluoro(phenylsulfonyl)methylation of carbonyls with PhSO2CF2H reagent in the presence of in situ generated substoichiometric amount of base

  摘要：

  The reactions between carbonyl compounds and PhSO2CF2H using substoichiometric amount of base in situ generated from N(TMS)(3) and catalytic amount of Me4NF have been investigated. It is found that both enolizable and non-enolizable aldehydes are suitable substrates to undergo nucleophilic difluoro(phenylsulfonyl)methylation. Compared to the previously reported trifluoromethylation of carbonyls with CF3H under the similar reaction conditions, the unique reactivity of PhSO2CF2H is attributed to its higher acidity than CF3H and the reversibility of its addition reaction with ketones under basic conditions. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2013.05.015

文献信息

• 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。
• US4837327A
  申请人：——

  公开号：US4837327A

  公开（公告）日：1989-06-06
• US4999429A
  申请人：——

  公开号：US4999429A

  公开（公告）日：1991-03-12
• US5175302A
  申请人：——

  公开号：US5175302A

  公开（公告）日：1992-12-29
• Nucleophilic difluoro(phenylsulfonyl)methylation of carbonyls with PhSO2CF2H reagent in the presence of in situ generated substoichiometric amount of base
  作者：Mingyou Hu、Bing Gao、Chuanfa Ni、Laijun Zhang、Jinbo Hu

  DOI：10.1016/j.jfluchem.2013.05.015

  日期：2013.11

  The reactions between carbonyl compounds and PhSO2CF2H using substoichiometric amount of base in situ generated from N(TMS)(3) and catalytic amount of Me4NF have been investigated. It is found that both enolizable and non-enolizable aldehydes are suitable substrates to undergo nucleophilic difluoro(phenylsulfonyl)methylation. Compared to the previously reported trifluoromethylation of carbonyls with CF3H under the similar reaction conditions, the unique reactivity of PhSO2CF2H is attributed to its higher acidity than CF3H and the reversibility of its addition reaction with ketones under basic conditions. (C) 2013 Elsevier B.V. All rights reserved.