1,1-difluoro-3-methyl-1-(phenylsulfonyl)butan-2-ol | 122590-91-4

• 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: 1,1-difluoro-3-methyl-1-(phenylsulfonyl)butan-2-ol
• 英文别名: 1-(benzenesulfonyl)-1,1-difluoro-3-methylbutan-2-ol
• CAS: 122590-91-4
• 化学式: C₁₁H₁₄F₂O₃S
• 分子量: 264.293
• InChiKey: FAAQCAIAIFVXFN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  1,1-difluoro-3-methyl-1-(phenylsulfonyl)butan-2-ol 在 盐酸 、 titanium(IV) tetraethanolate 、 草酰氯 、 二甲基亚砜 、 三乙胺 、 cesium fluoride 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 二氯甲烷 、 乙腈 为溶剂， 反应 61.0h， 生成 (1S,3R)-3-[difluoro(phenylsulfonyl)methyl]-3-isopropyl-2,3-dihydrobenzo[d]isothiazole 1-oxide
  参考文献：
  名称：

  N-叔丁烷亚磺酰基亚胺向芳烃的立体选择性[3 + 2]环加成反应，由可移动的PhSO（2）CF（2）基团促进：环亚砜亚胺的合成和转化。

  摘要：

  N-叔丁烷亚磺酰基亚胺和芳烃之间空前的[3 + 2]环加成反应为合成环亚砜亚胺提供了立体选择方法。二氟（苯磺酰基）甲基不仅在促进环加成反应中起重要作用，还可以通过将二氟化环亚砜亚胺转化为环亚磺酰胺而被除去或取代。

  DOI：

  10.1039/c4cc05042h
• 作为产物：
  描述：

  二氟甲基苯砜 在 四甲基氟化铵 、 四丁基氟化铵 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 20.5h， 生成 1,1-difluoro-3-methyl-1-(phenylsulfonyl)butan-2-ol
  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

• 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。
• Preparation of 1-aryl-2,2-difluoro enol esters via dehydrosulfonylation of α-(phenylsulfonyl)difluoromethylated benzoates
  作者：Laijun Zhang、Ya Li、Jinbo Hu

  DOI：10.1016/j.jfluchem.2007.03.004

  日期：2007.7

  1-Aryl-2,2-difluoro enol benzoates 4 has been prepared from α-(phenylsulfonyl)-difluoromethylated benzoates 3, which can be readily obtained from the reactions between simple aldehydes and PhSO2CF2H (or TMSCF2SO2Ph). 2,2-Difluoro enol esters 4 are relatively more stable compounds than 2,2-difluoro enol sily ethers, and they promise to act as interesting fluorinated building blocks for further elaborations

  由α-（苯磺酰基）-二氟甲基化的苯甲酸酯3制备了1-芳基-2,2-二氟烯醇苯甲酸酯4，可以通过简单的醛与PhSO 2 CF 2 H（或TMSCF 2 SO 2 Ph ）。2，2-二氟烯醇酯4是比2，2-二氟烯醇硅醚相对更稳定的化合物，它们有望作为有趣的氟化结构单元进行进一步的修饰。
• 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。
• Nucleophilic difluoromethylation of carbonyl compounds using TMSCF2SO2Ph and Mg0-mediated desulfonylation
  作者：Chuanfa Ni、Jinbo Hu

  DOI：10.1016/j.tetlet.2005.09.162

  日期：2005.11

  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.