3,3,4,4,4-Pentafluoro-1-((R)-toluene-4-sulfinyl)-butan-2-one | 167010-73-3

• 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: 3,3,4,4,4-Pentafluoro-1-((R)-toluene-4-sulfinyl)-butan-2-one
• 英文别名: 3,3,4,4,4-Pentafluoro-1-[(R)-4-methylbenzene-1-sulfinyl]butan-2-one；3,3,4,4,4-pentafluoro-1-[(R)-(4-methylphenyl)sulfinyl]butan-2-one
• CAS: 167010-73-3
• 化学式: C₁₁H₉F₅O₂S
• 分子量: 300.249
• InChiKey: BQSGLIILALRGIG-LJQANCHMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  53.4
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  3,3,4,4,4-Pentafluoro-1-((R)-toluene-4-sulfinyl)-butan-2-one 、 四苯基氨化膦 以 苯 为溶剂， 以76%的产率得到[2,2,3,3,3-Pentafluoro-1-((R)-toluene-4-sulfinylmethyl)-prop-(Z)-ylidene]-phenyl-amine
  参考文献：
  名称：

  Two Practical and Efficient Approaches to Fluorinated and Nonfluorinated Chiral β-Imino Sulfoxides

  摘要：

  Reaction of fluorinated and nonfluorinated N-substituted imidoyl chlorides 1 with lithium derivatives of enantiopure methyl p-tolyl sulfoxide 2a (or racemic methyl phenyl sulfoxide 2b) gave a wi;ie variety of chiral N-substituted beta-imino sulfoxides 4 in good to excellent yields. The title compounds (R)-4 were also prepared by aza-Wittig reaction of gamma-fluoro-beta-keto sulfoxides (R)-5 and N-aryl iminophosphoranes 6. The imino-enamino equilibrium was studied, showing, in all instances, the imino form as the predominant tautomer independent of the nature of the N-substituent. The configuration of the C=N double bond was found to be Z for both N-alkyl and N-aryl derivatives on the basis of H-1 NMR NOE difference experiments performed over several compounds. Ab initio calculations (HF/6-31G*) carried out on several representative examples of 1 and 4 are, in general, consistent with the experimental results.

  DOI：

  10.1021/jo980336f

文献信息

• New Versatile Fluorinated Chiral Building Blocks:  Synthesis and Reactivity of Optically Pure α-(Fluoroalkyl)-β-sulfinylenamines
  作者：Alberto Arnone、Pierfrancesco Bravo、Silvia Capelli、Giovanni Fronza、Stefano V. Meille、Matteo Zanda、Giancarlo Cavicchio、Marcello Crucianelli

  DOI：10.1021/jo952097r

  日期：1996.1.1

  Efficient synthesis of optically pure alpha-(fluoroalkyl)-beta-sulfinyl enamines has been achieved by aza-Wittig reaction of triphenyliminophosphoranes with the corresponding alpha-fluorinated-alpha'-sulfinyl ketones. The title compounds 3,4 showed an overwhelming preference for the Z stereochemistry of the enamine form. Their general reactivity has been studied. The reaction with some electrophiles (i.e. benzyl chloroformate and benzyl and allyl bromide) occurs at the nitrogen atom providing the corresponding N,N-disubstituted enamines. Nucleophiles add smoothly to C-2: heteroatom-centered nucleophiles like methanol, ammonia, and thiophenol afford gem-disubstituted derivatives under thermodynamic control, while a C-centered nucleophile like nitromethane adds in irreversible fashion. The hydride- and deuteride-promoted reduction of 3,4 to the N-Cbz-protected (14) and N-unprotected (15) alpha-fluorinated-alpha'-sulfinyl amines has been studied. Hydride addition was stereoselective, while low stereoselection was obtained with the other tested nucleophiles. Desulfurization of the optically pure 1,1,1-trifluoro-3-sulfinyl amine 15a afforded (R)-1-(trifluoromethyl)ethylamine 17. The Pummerer rearrangement of 14 occurs in an unusual nonoxidative way affording the sulfenamide 24, that readily provided (R)-(2-H)- and -(2-D)-3,3,3-trifluoroalaninol (19) and (R)-3,3,3-trifluoroalanine (22).
• Fluorinated enol ethers bearing chiral arylsulphinyl groups
  作者：Pierfrancesco Bravo、Luca Bruché、Marcello Crucianelli、Annamaria Merli

  DOI：10.1016/0022-1139(95)03262-c

  日期：1995.9

  A synthesis of 2-alkoxy-2-fluoroalkyl-1-(p-tolylsulphinyl) ethenes 4 with good regioselectivity from gamma-fluorosubstituted beta-ketosulphoxides 3 is described
• Two Practical and Efficient Approaches to Fluorinated and Nonfluorinated Chiral β-Imino Sulfoxides
  作者：Santos Fustero、Antonio Navarro、Belén Pina、Amparo Asensio、Pierfrancesco Bravo、Marcello Crucianelli、Alessandro Volonterio、Matteo Zanda

  DOI：10.1021/jo980336f

  日期：1998.9.1

  Reaction of fluorinated and nonfluorinated N-substituted imidoyl chlorides 1 with lithium derivatives of enantiopure methyl p-tolyl sulfoxide 2a (or racemic methyl phenyl sulfoxide 2b) gave a wi;ie variety of chiral N-substituted beta-imino sulfoxides 4 in good to excellent yields. The title compounds (R)-4 were also prepared by aza-Wittig reaction of gamma-fluoro-beta-keto sulfoxides (R)-5 and N-aryl iminophosphoranes 6. The imino-enamino equilibrium was studied, showing, in all instances, the imino form as the predominant tautomer independent of the nature of the N-substituent. The configuration of the C=N double bond was found to be Z for both N-alkyl and N-aryl derivatives on the basis of H-1 NMR NOE difference experiments performed over several compounds. Ab initio calculations (HF/6-31G*) carried out on several representative examples of 1 and 4 are, in general, consistent with the experimental results.