Ethyl 2,2-difluoro-3-hydroxy-3,3-diphenylpropanoate | 156544-73-9

• 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: Ethyl 2,2-difluoro-3-hydroxy-3,3-diphenylpropanoate
• CAS: 156544-73-9
• 化学式: C₁₇H₁₆F₂O₃
• 分子量: 306.309
• InChiKey: RVDLUTARUJUDPZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Ethyl 2,2-difluoro-3-hydroxy-3,3-diphenylpropanoate 在 吡啶 、 sodium hydroxide 、 苯磺酰氯 作用下， 反应 24.0h， 生成 1,1-difluoro-2,2-diphenylethylene
  参考文献：
  名称：

  通过α，α-二氟-β-内酯合成1,1-二氟烯烃

  摘要：

  提出了一种由酮一般合成1,1-二氟烯烃的新方法。该方法包括将酮与二氟Reformatsky试剂进行初始缩合，水解形成α，α-二氟-β-羟基酸，然后环化生成新型α，α-二氟-β-内酯。然后将它们热脱羧以形成1，1-二氟烯烃。

  DOI：

  10.1016/s0022-1139(97)00134-6
• 作为产物：
  描述：

  二苯甲酮 、 二氟溴乙酸乙酯 在 samarium diiodide 作用下， 以 四氢呋喃 为溶剂， 以47%的产率得到Ethyl 2,2-difluoro-3-hydroxy-3,3-diphenylpropanoate
  参考文献：
  名称：

  Nucleophilic introduction of fluorinated alkyl groups into aldehydes and ketones using the corresponding alkyl halide with samarium(II) iodide

  摘要：

  氟代烷基如PhCF2、C6F13、CF3CCl2和CF2CO2Et可以通过氟代烷基卤化物与SmI2在室温下有效反应，亲核引入醛或酮中，形成相应的醇。此外，通过卤化物与SmI2在硅氯化物存在下的反应，实现了PhCF2SiMe3、C6F13SiMe3和C6F13SiMe2Pri的合成；由此得到的氟代烷基硅化合物作为亲核氟代烷基化的试剂。2-氯-3,3,3-三氟丙烯衍生物也通过CF3CCl3与过量的SmI2在醛和PriOH存在下的反应选择性制备。

  DOI：

  10.1039/a606048j

文献信息

• Practically useful Reformatsky Type Reactions of Chlorodifluoroacetate and Bromodifluoroacetate Induced by Samarium(II) Diiodide
  作者：Masato Yoshida、Daiki Suzuki、Masahiko Iyoda

  DOI：10.1080/00397919608004565

  日期：1996.7

  Abstract Treatment of XCF2COOEt (X = Cl and Br) with SmI2 in THF gave efficiently β,β-difluorinated enolate equivalent, which was used for Reformatsky type reaction with aldehydes and ketones to give 2,2-difluoro-3-hydroxy ester.

  摘要 在 THF 中用 SmI2 处理 XCF2COOEt（X = Cl 和 Br）得到有效的 β,β-二氟烯醇化物等价物，用于与醛和酮的 Reformatsky 型反应，得到 2,2-二氟-3-羟基酯。
• An effective synthesis of 2,2-difluoro-3-hydroxy esters
  作者：Yanchang Shen、Ming Qi

  DOI：10.1016/0022-1139(93)02961-d

  日期：1994.6

  Reformatsky reactions of bromodifluoroacetate with carbonyl compounds and its applications to the synthesis of 2,2-difluoro-3-hydroxy esters as a means of two-carbon homologation with a difluoro moiety under mild conditions in good to excellent yields are described. In the case of aldehydes and aromatic ketones no catalyst was needed, while in the case of aliphatic ketones, 2 mol% of CeCl3 catalyst raises the yields dramatically from 30%-32% to 89%-92%.
• Rhodium-catalyzed Reformatsky-type reaction of ethyl bromodifluoroacetate
  作者：Kazuyuki Sato、Atsushi Tarui、Tetsuya Kita、Yoshitaka Ishida、Hanae Tamura、Masaaki Omote、Akira Ando、Itsumaro Kumadaki

  DOI：10.1016/j.tetlet.2004.05.099

  日期：2004.7

  Treatment of a variety of carbonyl compounds with ethyl bromodifluoroacetate and Et2Zn in the presence of RhCl(PPh3)(3) in CH3CN afforded Reformatsky-type products in good to excellent yields in a mild reaction condition. This is a good method to obtain a beta-hydroxy-alpha,alpha-difluoro carboxylic acid ethyl ester and especially to improve the poor reactivity of ketones. (C) 2004 Elsevier Ltd. All rights reserved.
• Nucleophilic introduction of fluorinated alkyl groups into aldehydes and ketones using the corresponding alkyl halide with samarium(II) iodide
  作者：Masato Yoshida、Daiki Suzuki、Masahiko Iyoda

  DOI：10.1039/a606048j

  日期：——

  Fluorinated alkyl groups such as PhCF2, C6F13, CF3CCl2 and CF2CO2Et are nucleophilically introduced into an aldehyde or ketone using fluorinated alkyl halides with SmI2; the reaction proceeds effectively at room temperature to give the corresponding alcohol. Furthermore, the synthesis of PhCF2SiMe3, C6F13SiMe3 and C6F13SiMe2Pri is achieved by reaction of the halide with SmI2 in the presence of the silyl chloride; the resultant fluoroalkylated silyl compounds are used as reagents for nucleophilic fluoroalkylation. 2-Chloro-3,3,3-trifluoropropene derivatives are also prepared selectively by the reaction of CF3CCl3 with an excess of SmI2 in the presence of an aldehyde and PriOH.

  氟代烷基如PhCF2、C6F13、CF3CCl2和CF2CO2Et可以通过氟代烷基卤化物与SmI2在室温下有效反应，亲核引入醛或酮中，形成相应的醇。此外，通过卤化物与SmI2在硅氯化物存在下的反应，实现了PhCF2SiMe3、C6F13SiMe3和C6F13SiMe2Pri的合成；由此得到的氟代烷基硅化合物作为亲核氟代烷基化的试剂。2-氯-3,3,3-三氟丙烯衍生物也通过CF3CCl3与过量的SmI2在醛和PriOH存在下的反应选择性制备。
• Synthesis of 1,1-difluoroalkenes via α,α-difluoro-β-lactones
  作者：Rogelio Ocampo、William R. Dolbier、Rodrigo Paredes

  DOI：10.1016/s0022-1139(97)00134-6

  日期：1998.2

  A new method for the general synthesis of 1,1-difluoroalkenes from ketones is presented. The procedure involves initial condensation of a ketone with the difluoro Reformatsky reagent, hydrolysis to form the α,α-difluoro-β-hydroxy acids, followed by cyclization to make the novel α,α-difluoro-β-lactones. These are then thermally decarboxylated to form the 1,1-difluoroalkenes.

  提出了一种由酮一般合成1,1-二氟烯烃的新方法。该方法包括将酮与二氟Reformatsky试剂进行初始缩合，水解形成α，α-二氟-β-羟基酸，然后环化生成新型α，α-二氟-β-内酯。然后将它们热脱羧以形成1，1-二氟烯烃。