4-chlorophenyl 4-bromobenzoate | 33696-03-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 缩酚酸和缩酚酸环醚类
• 英文名称: 4-chlorophenyl 4-bromobenzoate
• 英文别名: 4-Bromo-benzoic acid 4-chloro-phenyl ester；(4-chlorophenyl) 4-bromobenzoate
• CAS: 33696-03-6
• 化学式: C₁₃H₈BrClO₂
• 分子量: 311.562
• InChiKey: QXIDVEOEJTUBFQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-chlorophenyl 4-bromobenzoate 、 ethyl 3-bromo-2-(dibenzylamino)hexanoate 在 乙二醇二甲醚溴化镍 、 potassium phosphate 、 三聚氰胺 、 4,4'-二甲氧基-2,2'-联吡啶 、 magnesium chloride 、 锌 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 24.0h， 以62%的产率得到4-chlorophenyl 4-((benzyl(1-ethoxy-1-oxo-3-phenylhexan-2-yl)amino)methyl)benzoate
  参考文献：
  名称：

  自由基 1,4-芳基迁移使 α-氨基-β-溴酸酯与芳基溴的远程交叉电偶偶联成为可能

  摘要：

  我们报告了一种前所未有的、高效的镍催化自由基中继，用于通过 1,4-芳基迁移/芳基化级联将 β-溴-α-苄基氨基酸酯与芳基溴进行远程交叉亲电偶联。β-溴-α-苄基氨基酸酯被认为是独特的分子支架，允许芳基迁移反应，这是自由基休战-微笑重排的概念新变体。该反应能够使用具有广泛底物范围和优异非对映选择性的长期稳定的 Ni/联吡啶/Zn 系统形成两个新的 C(sp 3 )-C(sp 2 ) 键，为远程芳基提供了一个有效的平台氨基酸酯通过氧化还原中性 C(sp 3 )-C(sp 2 ) 的迁移和芳基化) 键断裂。机械地，该级联反应由通过C（SP的产生相结合自由交亲电耦合和自由基1,4-芳迁移的两个强大的催化循环实现3）-centred从C的均裂自由基中间体（SP 3） -Br 键和瞬态烷基自由基转换为强大的 α-氨基烷基自由基。

  DOI：

  10.1002/anie.202106273
• 作为产物：
  描述：

  4-溴苯甲酸 在 氯化亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 生成 4-chlorophenyl 4-bromobenzoate
  参考文献：
  名称：

  Crystal Engineering of Hand-Twisted Helical Crystals

  摘要：

  A strategy is outlined for the design of hand-twisted helical crystals. The starting point in the exercise is the one-dimensional (1D) plastic crystal, 1,4-dibromobenzene, which is then changed to a 1D elastic crystal, exemplified by 4-bromophenyl 4'-chlorobenzoate, by introduction of a molecular synthon-O-CO- in lieu of the supramolecular synthon Br center dot center dot center dot Br in the precursor. The 1D elastic crystals are next modified to two-dimensional (2D) elastic crystals, of the type 4-bromophenyl 4'-nitrobenzoate where the halogen bonding and C-H center dot center dot center dot O hydrogen bonding are well-matched. Finally, varying the interaction strengths in these 2D elastic crystals gives plastic crystals with two pairs of bendable faces but without slip planes. Typical examples are 4-chlorophenyl and 4-bromophenyl 4'-nitrobenzoate. This type of 2D plasticity represents a new type of bendable crystals in which plastic behavior is seen with a fair degree of isotropic character in the crystal packing. The presence of two sets of bendable faces, generally orthogonal to each other, allows for the possibility of hand-twisting of the crystals to give grossly helical morphologies. Accordingly, we propose the name hand-twisted helical crystals for these substances.

  DOI：

  10.1021/jacs.6b11835

文献信息

• Copper-Catalyzed Regioselective Sila-Acylation and Silaformylation of 1,3-Dienes Using Esters
  作者：Kazutaka Kanayama、Ayumi Sawada、Katsushi Suda、Tetsuaki Fujihara

  DOI：10.1021/acs.joc.1c00945

  日期：2021.7.16

  The regioselective sila-acylation and silaformylation of 1,3-dienes was achieved over a copper catalyst using a silylborane as a silyl source. β,γ-Unsaturated ketones with a (dimethylphenylsilyl)methyl moiety at the α-position were obtained using esters, while β,γ-unsaturated aldehydes were obtained using formate esters.

  使用甲硅烷基硼烷作为甲硅烷基源，在铜催化剂上实现了 1,3-二烯的区域选择性甲硅烷基化和甲硅烷基化。使用酯获得在 α 位具有（二甲基苯基甲硅烷基）甲基部分的 β,γ-不饱和酮，而使用甲酸酯获得 β,γ-不饱和醛。
• Copper-Catalyzed Regioselective Sila-acylation and Sila-imination of Allenes Using Esters and Nitriles
  作者：Tetsuaki Fujihara、Katsushi Suda、Yuki Matsuda、Tatsuya Yamaguchi

  DOI：10.1055/a-1648-7154

  日期：2022.2

  presence of a copper catalyst using PhMe2Si-B(pin) and esters as the silyl and acyl sources, respectively. β-Silyl-β,γ-unsaturated ketones are obtained regioselectively in good to high yields. The sila-imination of allenes is also achieved using nitriles as electrophiles. Exposure of the reaction mixture to air results in the production of cyclic silyl peroxides.

  丙二烯的硅烷酰化是在铜催化剂存在下使用 PhMe2Si-B(pin) 和酯分别作为甲硅烷基和酰基来源进行的。β-甲硅烷基-β,γ-不饱和酮以良好到高产率的区域选择性获得。使用腈作为亲电试剂也可以实现丙二烯的硅烷化。将反应混合物暴露在空气中会产生环状过氧化甲硅烷。
• Cu-catalyzed enantioselective synthesis of tertiary benzylic copper complexes and their <i>in situ</i> addition to carbonyl compounds
  作者：Fengchang Cheng、Wenxin Lu、Wei Huang、Lu Wen、Mingfeng Li、Fanke Meng

  DOI：10.1039/c8sc00827b

  日期：——

  tertiary benzylic copper complexes from Cu–B(pin) (pin = pinacolato) additions to 1,1-disubstituted alkenes followed by in situ reactions with ketones and carboxylic acid phenol esters to construct multifunctional alkylboron compounds that contain quaternary stereogenic centers is presented. The method is distinguished by the unprecedented reaction mode of tertiary benzylic Cu complexes, allowing reaction

  通过 Cu-B(pin)（pin = pinacolato）加成到 1,1-二取代烯烃上，催化化学和对映选择性生成叔苄基铜配合物，然后与酮和羧酸苯酚酯进行原位反应，构建包含以下成分的多功能烷基硼化合物：提出了四级立体中心。该方法的特点是叔苄基铜配合物的前所未有的反应模式，允许与各种羰基亲电子试剂以良好的产率进行反应，并具有高化学选择性、位点选择性、非对映选择性和对映选择性。催化方案是在环境温度下使用易于获得的手性配体和铜盐进行的。多功能烷基硼产品的官能化提供了难以获得的有用的结构单元。
• A phosphine sulfide, a manufacturing process therefor and a use thereof
  申请人：MITSUI CHEMICALS, INC.

  公开号：EP0972776A1

  公开（公告）日：2000-01-19

  A basic organic compound which is soluble in an organic solvent, does not have problems in its preparation or handling and exhibits catalytic activity as a basic compound, is a phosphine sulfide represented by the (1): The phosphine sulfide represented by formula (1), is made by reacting one molecule of thiophosphoryl chloride with three molecules of a phosphorane represented by formula (2): A process for effectively manufacturing a poly(alkylene oxide) involves polymerizing an alkylene oxide in the presence of the above organic compound (phosphine sulfide), or in the presence of the phosphine sulfide and an active hydrogen compound selected from water and organic compounds having a partial structure of -OH or -NH-. A process for manufacturing a 1,2-dioxyethane derivative from an epoxy compound, i.e. manufacturing a 1,2-dioxyethane derivative involves reacting an epoxy compound with a carboxylate, carboxylic anhydride, carbonate or phenol compound, respectively, in the presence of the phosphine sulfide.

  一种可溶于有机溶剂、在制备或处理过程中不会出现问题并具有催化活性的碱性有机化合物是硫化膦，其代表式为（1）： 式（1）代表的硫化膦是由一分子硫代磷酰氯与三分子式（2）代表的磷烷反应制得的： 一种有效制造聚环氧亚烷烃的工艺是在上述有机化合物（硫化膦）存在下，或在硫化膦和选 自水和部分结构为-OH 或-NH-的有机化合物的活性氢化合物存在下，聚合环氧亚烷烃。 由环氧化合物制造 1，2-二氧乙烷衍生物的工艺，即制造 1，2-二氧乙烷衍生物的工艺包括在硫化膦存在下，环氧化合物分别与羧酸盐、羧酸酐、碳酸盐或苯酚化合物反应。
• Kinetics of the reaction of 4-nitrophenyl benzoates with 4-chlorophenol in the presence of potassium carbonate in dimethylformamide
  作者：I. A. Os’kina、V. M. Vlasov

  DOI：10.1134/s1070428006060091

  日期：2006.6

  The effect of the substituent in the benzoyl group on the relative rate and activation parameters of transesterification of substituted 4-nitrophenyl benzoates with 4-chlorophenol in dimethylformamide in the presence of potassium carbonate was studied by the competing reaction technique. The whole series of benzoates showed the enthalpy-entropy compensation effect. 4-Nitrophenyl benzoates having electron-acceptor substituents give rise to isokinetic relationship with an isokinetic temperature beta of 382 K. The mechanism of the transesterification process is discussed.