4-氯-1-(间甲基苯基)-1-丁酮 | 40877-15-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 4-氯-1-(间甲基苯基)-1-丁酮
• 英文名称: 4-chloro-1-(m-tolyl)butan-1-one
• 英文别名: 4-Chloro-1-m-tolylbutan-1-one；4-chloro-1-(3-methylphenyl)butan-1-one
• CAS: 40877-15-4
• 化学式: C₁₁H₁₃ClO
• 分子量: 196.677
• InChiKey: FGISHBQXRZRKJX-UHFFFAOYSA-N

物化性质

• 沸点：
  128-130 °C(Press: 4 Torr)
• 密度：
  1.0730 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  13
• 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：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-氯-1-(间甲基苯基)-1-丁酮 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 12.0h， 以91%的产率得到环丙基(3-甲基苯基)甲酮
  参考文献：
  名称：

  Precise control of the formation of a covalent and an ionic bond in carbocation-carbanion combination reactions

  摘要：

  The electronic effect on the selectivity of covalent or ionic bond formation was examined for the reaction of Kuhn's anion 1- (C67H39-; tris(7H-dibenzo[c,g]fluorenylidenemethyl)methide ion) and 1-aryl-2,3-dicyclopropylcyclopropenylium ions. The carbocation stability was progressively changed by varying the substituent on the phenyl ring, while the steric effect was kept essentially unchanged. The cations having the p-chlorophenyl (2a+), phenyl (2b+), m-methylphenyl (2c+), or m,m'-dimethylphenyl (2d+) group gave a covalent product, whereas a carbocation-carbanion salt was obtained from the cations having the p-methylphenyl (2e+) or p-methoxyphenyl (2f+) group. The reduction potentials E(red) of the cations, as determined by cyclic voltammetry, showed that the formation of the covalent or ionic product is switched by a small difference in stability (less-than-or-equal-to 0.4 kcal/mol) between 2d+ and 2e+. In chloroform, the salts 1-2e+ and 1-2f+ were transformed into covalent forms 1-2e and 1-2f, which can exist only in solution. When 1-(2a-d) and 1-2e,f+ were dissolved in DMSO, equilibrium between a covalent compound and ions was established. A plot of the free energy of heterolysis DELTAG(het)-degrees for 1-(2a-f) against the E(red) of the corresponding cations 2a-f+ showed that DELTAG(het)-degrees decreases as the cation is more stabilized. The heterolysis in DMSO was shown to be enhanced by ca. 13 kcal/mol both by the steric congestion in the covalent molecules and the stabilization of the cyclopropenylium ions by solvation.

  DOI：

  10.1021/jo00073a047
• 作为产物：
  描述：

  3-溴甲基苯 在 manganese(II) triflate 、 碘 、 lithium perchlorate 、 magnesium 、 溶剂黄146 、 magnesium chloride 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 3.5h， 生成 4-氯-1-(间甲基苯基)-1-丁酮
  参考文献：
  名称：

  锰催化的烷氧基自由基对环烷醇的电化学解构氯化反应。

  摘要：

  已经开发了锰催化的环烷醇的电化学解构氯化法。这种电化学方法可从醇中获得烷氧基，并具有广泛的底物范围，可将各种环丙醇和环丁醇转化为可合成使用的β-和γ-氯化酮（40个实例）。此外，采用循环流电化学和连续在线纯化的组合以克为单位获得产物。

  DOI：

  10.1021/acs.orglett.9b03652

文献信息

• NOVEL TRPV3 MODULATORS
  申请人：AbbVie Inc.

  公开号：US20130131036A1

  公开（公告）日：2013-05-23

  Disclosed herein are modulators of TRPV3 of formula (II): wherein G 1 , X 1 , X 2 , X 3 , X 4 , X 5 , G 2 , R a , R b , and u are as defined in the specification. Compositions comprising such compounds and methods for treating conditions and disorders using such compounds and compositions are also presented.

  本文披露了公式（II）的TRPV3调节剂： 其中G1、X1、X2、X3、X4、X5、G2、Ra、Rb和u的定义如规范中所述。还提供了包含这些化合物的组合物以及使用这些化合物和组合物治疗疾病和疾病的方法。
• Catalytic Asymmetric Intramolecular Homologation of Ketones with α-Diazoesters: Synthesis of Cyclic α-Aryl/Alkyl β-Ketoesters
  作者：Wei Li、Fei Tan、Xiaoyu Hao、Gang Wang、Yu Tang、Xiaohua Liu、Lili Lin、Xiaoming Feng

  DOI：10.1002/anie.201409572

  日期：2015.1.26

  A catalytic asymmetric intramolecular homologation of simple ketones with α‐diazoesters was firstly accomplished with a chiral N,N′‐dioxide–Sc(OTf)3 complex. This method provides an efficient access to chiral cyclic α‐aryl/alkyl β‐ketoesters containing an all‐carbon quaternary stereocenter. Under mild conditions, a variety of aryl‐ and alkyl‐substituted ketone groups reacted with α‐diazoester groups

  首先用手性N，N'-二氧化物-Sc（OTf）3配合物完成了简单的酮与α-重氮化合物的催化不对称分子内同源性。这种方法可以有效地获得含有全碳季立体中心的手性环状α-芳基/烷基β-酮酸酯。在温和的条件下，各种芳基和烷基取代的酮基通过分子内加成/重排过程与α-重氮酸酯基团平稳反应，从而以高收率和对映体过量生成β-酮酸酯。
• TRPV3 modulators
  申请人：AbbVie Inc.

  公开号：US08772500B2

  公开（公告）日：2014-07-08

  Disclosed herein are modulators of TRPV3 of formula (II): wherein G1, X1, X2, X3, X4, X5, G2, Ra, Rb, and u are as defined in the specification. Compositions comprising such compounds and methods for treating conditions and disorders using such compounds and compositions are also presented.

  本文披露了TRPV3的调节剂的公式(II)：其中G1、X1、X2、X3、X4、X5、G2、Ra、Rb和u如规范中所定义。还提供了包含这些化合物的组合物和使用这些化合物和组合物治疗疾病和疾病的方法。
• Chemoselective and Divergent Synthesis of Chlorohydrins and Oxaheterocycles via Ir-Catalyzed Asymmetric Hydrogenation
  作者：Yan Zong、Xiaomei Zou、Jingyuan Song、Gen-Qiang Chen、Xumu Zhang

  DOI：10.1021/acs.orglett.3c02565

  日期：2023.9.22

  Chlorohydrins and oxaheterocycles are synthetically valuable building blocks for diverse natural products and therapeutic substances. A highly efficient Ir/f-phamidol-catalyzed asymmetric hydrogenation of ω-chloroketones was successfully developed, and various chlorohydrins and oxaheterocycles were obtained divergently with excellent yields and enantioselectivities (up to >99% yield and >99% ee). Synthetic

  氯醇和氧杂环是多种天然产物和治疗物质的具有合成价值的结构单元。成功开发了高效的Ir/ f-邻氨基醇催化的ω-氯酮不对称氢化反应，并以优异的产率和对映选择性（高达>99%产率和>99%ee）不同地获得了各种氯代醇和氧杂环。通过这种催化方法对几种对映体富集的药物的关键中间体进行克级合成，证明了这种发散转化的合成效用。
• [EN] METHANOL DERIVATIVES AS TRPV3 MODULATORS<br/>[FR] NOUVEAUX MODULATEURS DE TRPV3
  申请人：ABBVIE INC

  公开号：WO2013062966A3

  公开（公告）日：2013-08-22