4,4,4-trifluoro-3-hydroxy-1-phenylbutan-2-one | 121194-38-5

• 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: 4,4,4-trifluoro-3-hydroxy-1-phenylbutan-2-one
• 英文别名: 4,4,4-trifluoro-3-hydroxy-1-phenyl-2-butanone；2-Butanone, 4,4,4-trifluoro-3-hydroxy-1-phenyl-
• CAS: 121194-38-5
• 化学式: C₁₀H₉F₃O₂
• 分子量: 218.175
• InChiKey: YZAROGYWBITELL-UHFFFAOYSA-N

物化性质

• 熔点：
  86 °C(Solv: cyclohexane (110-82-7))
• 沸点：
  278.4±35.0 °C(Predicted)
• 密度：
  1.309±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4,4,4-trifluoro-3-hydroxy-1-phenylbutan-2-one 在 甲酸 、 N-[(1S,2S)-1,2-diphenyl-2-(3-phenylpropylamino)ethyl]-4-methylbenzene sulfonamide ammonium chloride ruthenium 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以95%的产率得到
  参考文献：
  名称：

  Noyori-Ikariya 催化剂的氢键能力能够通过动态动力学分辨率立体选择性地获得 CF3 取代的 syn-1,2-二醇

  摘要：

  立体纯CF 3取代的顺式-1,2-二醇通过HCO 2 H/Et 3 N中相应外消旋α-羟基酮的还原动态动力学拆分来制备。 (Het)芳基、苄基、乙烯基和烷基酮是可耐受的，提供 ≥95% ee 和 ≥87:13 syn / anti的产品。这种方法可以快速获得立体纯的生物活性分子。此外，对三种类型的Noyori-Ikariya钌催化剂进行了DFT计算，以显示它们通过氢键受体SO 2区域和CH/π相互作用引导立体选择性的一般能力。

  DOI：

  10.1021/acscatal.3c00980
• 作为产物：
  描述：

  (3RS)-2-氧代-4-苯基-3-(苯基羰基)氨基-1,1,1-三氟丁烷 在 盐酸 作用下， 生成 4,4,4-trifluoro-3-hydroxy-1-phenylbutan-2-one
  参考文献：
  名称：

  Synthesis of peptidyl fluoromethyl ketones and peptidyl .alpha.-keto esters as inhibitors of porcine pancreatic elastase, human neutrophil elastase, and rat and human neutrophil cathepsin G

  摘要：

  Comparison of MeO-Suc-Val-Pro-Phe-CO2Me (29) and MeO-Suc-Ala-Ala-Pro-Phe- CO2Me (25) with their corresponding trifluoromethyl ketones 9a and 9b, respectively, in rat and human neutrophil cathepsin G assays showed the alpha-keto esters to be more potent inhibitors. Likewise, Ac-Pro-Ala-Pro-Ala-CO2Me (21) was more potent than its corresponding trifluoromethyl ketone (9c) in both porcine pancreatic elastase and human neutrophil elastase assays. Within a set of Ala-Ala-Pro-Val-CF3 elastase inhibitors, the carbobenzyloxy (Cbz) N-protecting group conferred greater potency as a P5 site recognition unit for elastase than did dansyl, methoxysuccinyl, or tert-butyloxycarbonyl. Initial inhibition of elastase was greater when trifluoromethyl ketone 9f was added from a stock solution of dimethyl sulfoxide than when it had been buffer-equilibrated prior to assay, which suggests that the nonhydrated ketone is the more effective form of the inhibitor. The most potent elastase inhibitor we report is Na-(Ad-SO2)-N epsilon-(MeO-Suc)Lys-Pro-Val-CF3 (16) which has a Ki of 0.58 nM.

  DOI：

  10.1021/jm00163a063

文献信息

• Convenient Synthesis of .ALPHA.-Trifluoromethylated Acyloins from .ALPHA.-Hydroxy or .ALPHA.-Amino Acids.
  作者：Masami KAWASE、Setsuo SAITO、Teruo KURIHARA

  DOI：10.1248/cpb.48.1338

  日期：——

  acyloins (2 and 6) have been prepared from alpha-hydroxy acids (1), N-acylprolines (5) or N-acyl-N-alkyl alpha-amino acids (8) by novel transformation reactions with trifluoroacetic anhydride (TFAA) in the presence of pyridine. The former reaction of 1 could proceed through mesoionic 1,3-dioxolium-4-olates, whereas the latter two reactions of alpha-amino acids (5 and 8) could involve mesoionic 1,3-oxazolium-5-olates

  α-三氟甲基化酰基辅酶（2和6）是由α-羟基酸（1），N-酰基脯氨酸（5）或N-酰基-N-烷基α-氨基酸（8）与三氟乙酸酐（ TFAA）在吡啶存在下。前者1的反应可以通过1,3-二氧恶唑鎓4-olates进行，而后两个α-氨基酸（5和8）的反应可能涉及1,3-二恶唑鎓5-olates。1与TFAA的反应在实际应用中显示出更大的潜力，这是因为起始材料易于使用且易于操作。
• Unusual reactions of secondary amino acids with trifluoroacetic anhydride: A novel access to α-trifluoromethylated acyloins
  作者：Masami Kawase

  DOI：10.1016/0040-4039(94)88187-1

  日期：1994.1

  A new fragmentation reaction of secondary α-amino acids with trifluoroacetic anhydride under Dakin-West reaction conditions proceeds through oxazolium salt intermediates followed by ring cleavage to form α-trifluoromethylated acyloins in good yields.

  在Dakin-West反应条件下，仲α-氨基酸与三氟乙酸酐的新断裂反应通过恶唑鎓盐中间体进行，然后进行环裂解，以高收率形成α-三氟甲基化酰基辅酶。
• A convenient synthesis of α-trifluoremethylated and α-perfluoroalkylated acyloins from α-hydroxy acids
  作者：Masami Kawase、Teruo Kurihara

  DOI：10.1016/0040-4039(94)88284-3

  日期：1994.10

  A novel transformation of α-hydroxy acids to α-trifluoremethylated and α-perfluoroalkylated acyloins was efficiently realized by utilizing trifluoroacetic or perfluoroalkylcarboxylic anhydrides in the presence of pyridine, in which probable intermediates were meso-ionic 1,3-dioxolium-4-olates.

  通过在吡啶存在下利用三氟乙酸或全氟烷基羧酸酐，可以有效地实现α-羟基酸向α-三氟甲基化和α-全氟烷基化酰基转移的新型转化，其中可能的中间体是中离子1,3-二氧杂-4-醇盐。
• Oxidation of fluoroalkyl-substituted allylic alcohols: a synthesis of fluorinated ?,?-epoxyketones
  作者：V. G. Ratner、K. L. Pashkevieh

  DOI：10.1007/bf01435797

  日期：1996.3

  Fluoroalkyl-substituted allylic alcohols are readily and selectively oxidized at the hydroxyl group with the Swern or Dess-Martin reagents to give α,β-unsaturated ketones, and on treatment withm-chloroperbenzoic acid ortert-butyl hydroperoxide they are oxidized to the corresponding epoxyalcohols. The latter are oxidized by Swern or Dess-Martin reagents at the hydroxyl group to α,β-epoxyketones, which

  氟代烷基取代的烯丙醇很容易用 Swern 或 Dess-Martin 试剂在羟基处选择性氧化，得到 α,β-不饱和酮，在用间氯过苯甲酸或叔丁基氢过氧化物处理时，它们被氧化成相应的环氧醇。后者在羟基处被 Swern 或 Dess-Martin 试剂氧化成 α,β-环氧酮，形成在分离条件下稳定的水合物。
• Process for producing 4,4,4,- trifluoro-3-hydroxybutyric acid
  申请人：CENTRAL GLASS COMPANY, LIMITED

  公开号：US20030088095A1

  公开（公告）日：2003-05-08

  A first process for producing an optically active perfluoroalkylcarbinol derivative includes (a) reacting an optically active imine with a compound that is a hemiacetal of a perfluoroalkylaldehyde or a hydrate of a perfluoroalkylaldehyde to obtain a condensate; and (b) hydrolyzing the condensate under an acid condition. A second process for increasing optical purity of an optically active 4,4,4-trifluoro 3-hydroxy-1-aryl-1-butanone derivative includes (a) precipitating a racemic crystal of the derivative, from the derivative; and (b) removing the racemic crystal from the derivative. A third process for increasing optical purity of the butanone derivative includes recrystallizing the derivative. Novel compounds are optically active and inactive 4,4,4-trifluoro-3-hydroxybutanoic aryl ester derivatives. A fourth process for producing an optically active or optically inactive 4,4,4-trifluoro-3-hydroxybutyric acid aryl ester derivative includes oxidizing an optically active or optically inactive 4,4,4-trifluoro-3-hydroxy-1-aryl-1-butanone derivative. A fifth process for increasing optical purity of the optically active aryl ester derivative includes recrystallizing the derivative. A sixth process for producing an optically active 4,4,4-trifluoro-1,3-butanediol includes reducing the optically active aryl ester derivative by a hydride. A seventh process for producing an optically active or inactive 4,4,4-trifluoro-3-hydroxybutyric acid alkyl ester derivative includes reacting under an acid condition the optically active or optically inactive aryl ester derivative with a lower alcohol. It is possible to suitably combine at least two of the first to seventh processes.

  生产光学活性全氟烷基羟基甲基醇衍生物的第一种方法包括（a）将光学活性亚胺与半乙醇的全氟烷基醛或全氟烷基醛的水合物反应，以获得缩合物; （b）在酸性条件下水解缩合物。增加光学纯度的光学活性4,4,4-三氟-3-羟基-1-芳基-1-丁酮衍生物的第二种方法包括（a）从该衍生物中沉淀出外消旋晶体; （b）将外消旋晶体从衍生物中去除。增加丁酮衍生物光学纯度的第三种方法包括重结晶该衍生物。新化合物是光学活性和非活性的4,4,4-三氟-3-羟基丁酸芳基酯衍生物。生产光学活性或非活性的4,4,4-三氟-3-羟基丁酸芳基酯衍生物的第四种方法包括将光学活性或非活性的4,4,4-三氟-3-羟基-1-芳基-1-丁酮衍生物氧化。增加光学活性芳基酯衍生物光学纯度的第五种方法包括重结晶该衍生物。生产光学活性4,4,4-三氟-1,3-丁二醇的第六种方法包括通过氢化还原光学活性芳基酯衍生物。生产光学活性或非活性的4,4,4-三氟-3-羟基丁酸烷基酯衍生物的第七种方法包括在酸性条件下将光学活性或非活性的芳基酯衍生物与低级醇反应。可以适当地组合第一至第七种方法中的至少两种方法。