β-chlorobenzenepropanoic acid ethyl ester | 77085-24-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: β-chlorobenzenepropanoic acid ethyl ester
• 英文别名: ethyl 2-chloro-2-phenylpropanoate；ethyl 3-chloro-3-phenylpropanoate
• CAS: 77085-24-6
• 化学式: C₁₁H₁₃ClO₂
• 分子量: 212.676
• InChiKey: PXQAQGIZUIQDMA-UHFFFAOYSA-N

物化性质

• 沸点：
  80 °C(Press: 0.11 Torr)
• 密度：
  1.134±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  1-甲氧基-1-(三甲基甲硅氧基)-2-甲基-1-丙烯 、 β-chlorobenzenepropanoic acid ethyl ester 在 indium(III) bromide 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以82%的产率得到methyl 5-ethoxy-4-(ethoxycarbonyloxy)-2,2-dimethyl-5-oxo-3-phenylpentanoate
  参考文献：
  名称：

  三卤化铟催化烷基氯与烯丙基甲硅烷基酯的偶联反应。

  摘要：

  卤化铟（III）不仅催化烷基氯化物与衍生自酯，酮和醛的甲硅烷基烯醇酸酯的偶联，以生成各种α-烷基化的羰基化合物，而且还催化了烯醇乙醛，烷基氯的一锅三组分反应，以及烯丙基硅烷或炔基硅烷。

  DOI：

  10.1021/ol701684n
• 作为产物：
  描述：

  苯甲酰乙酸乙酯 在 indium(III) hydroxide 、 二甲基一氯硅烷 作用下， 以 氯仿 为溶剂， 反应 2.0h， 以64%的产率得到β-chlorobenzenepropanoic acid ethyl ester
  参考文献：
  名称：

  羰基化合物直接转化为有机卤化物：使用氯二甲基硅烷的氢氧化铟 (III) 催化脱氧卤化

  摘要：

  羰基化合物和氯二甲基硅烷的反应在氢氧化铟 (III) 的有效催化下得到相应的脱氧氯化产物，其中羰基碳接受两种亲核试剂（H 和 Cl）并释放氧。只有 In(OH)3 催化了反应，典型的路易斯酸如 TiCl4、AlCl3 和 BF3.OEt2 没有表现出催化活性。这种脱氧氯化的反应机理包括先氢化硅烷化，然后是氯化。其他亲核试剂如烯丙基或碘可用于该方法。铟催化剂的适度路易斯酸度使化学选择性反应成为可能，因此在反应过程中酯、硝基、氰基或卤素基团不受影响。

  DOI：

  10.1021/ja0283246

文献信息

• Desulfurative Chlorination of Alkyl Phenyl Sulfides
  作者：Daniele Canestrari、Stefano Lancianesi、Eider Badiola、Chiara Strinna、Hasim Ibrahim、Mauro F. A. Adamo

  DOI：10.1021/acs.orglett.7b00077

  日期：2017.2.17

  The chlorination of readily available secondary and tertiary alkyl phenyl sulfides using (dichloroiodo)benzene (PhICl2) is reported. This mild and rapid nucleophilic chlorination is extended to sulfa-Michael derived sulfides, affording elimination-sensitive β-chloro carbonyl and nitro compounds in good yields. The chlorination of enantioenriched benzylic sulfides to the corresponding inverted chlorides

  报道了使用（二氯碘代）苯（PhICl 2）对易得的仲和叔烷基苯基硫化物进行氯化。这种温和而快速的亲核氯化作用扩展到了磺胺-迈克尔衍生的硫化物，从而以高收率提供了对消除敏感的β-氯羰基和硝基化合物。将对映体富集的苄基硫化物氯化为相应的倒置氯化物，其立体定向性很高，因此可以正式进入对映体富集的氯-迈克尔加合物。这意味着一个二氯λ的地层中的装置4提出-sulfurane中间。
• Indium-catalyzed coupling reaction between silyl enolates and alkyl chlorides or alkyl ethers
  作者：Yoshihiro Nishimoto、Takahiro Saito、Makoto Yasuda、Akio Baba

  DOI：10.1016/j.tet.2009.03.106

  日期：2009.7

  The coupling reactions of alkyl chlorides with silyl enolates catalyzed by InBr3, and the coupling reactions of alkyl ethers with silyl enolates catalyzed by the combined Lewis acid of InBr3/Me3SiBr are described. In both reaction systems, various types of silyl enolates were used to give corresponding α-alkylated esters, ketones, carboxylic acids, amides, thioesters, and aldehydes.

  描述了烷基氯化物与InBr 3催化的烯醇硅酸酯的偶联反应，以及烷基醚与InBr 3 / Me 3 SiBr的路易斯酸催化的烯醇硅酸酯的偶联反应。在两个反应系统中，都使用了各种类型的甲硅烷基烯酸酯，以生成相应的α-烷基化的酯，酮，羧酸，酰胺，硫代酯和醛。
• Preparation and Reactions of Titanium(III) Chloride Solubilized in Inert Organic Solvents
  作者：Hitomi Suzuki、Hajime Manabe、Rika Enokiya、Yasuaki Hanazaki

  DOI：10.1246/cl.1986.1339

  日期：1986.8.5

  Titanium(IV) chloride reacts with dialkyl telluride in inert solvents such as dichloromethane or benzene to form a stable homogeneous solution of titanium(III) species. Reduction of several organic functionalities has been carried out using the low valent titanium solution thus obtained.

  氯化钛 (IV) 在惰性溶剂（如二氯甲烷或苯）中与二烷基碲化物反应，形成钛 (III) 物质的稳定均匀溶液。使用由此获得的低价钛溶液进行了几种有机官能团的还原。
• Indium-Catalyzed Direct Chlorination of Alcohols Using Chlorodimethylsilane−Benzil as a Selective and Mild System
  作者：Makoto Yasuda、Satoshi Yamasaki、Yoshiyuki Onishi、Akio Baba

  DOI：10.1021/ja048688t

  日期：2004.6.1

  The InCl3-catalyzed reaction of alcohols with chlorodimethylsilane (HSiMe2Cl) in the presence of benzil gave the corresponding organic chlorides under mild conditions. Benzil significantly changes the reaction course because the reducing product through dehydroxyhydration was obtained in the absence of benzil. The secondary or tertiary alcohols were effectively chlorinated. The substrates bearing acid-sensitive functional groups were also applied to this system. The highly selective chlorination of the tertiary site was observed in the competitive reaction between tertiary and primary alcohols. The highly coordinated hydrosilane generated from benzil and HSiMe2Cl is an important intermediate.
• Direct Reduction of Alcohols:  Highly Chemoselective Reducing System for Secondary or Tertiary Alcohols Using Chlorodiphenylsilane with a Catalytic Amount of Indium Trichloride
  作者：Makoto Yasuda、Yoshiyuki Onishi、Masako Ueba、Takashi Miyai、Akio Baba

  DOI：10.1021/jo0158534

  日期：2001.11.1

  The direct reduction of alcohols using chlorodiphenylsilane as a hydride source in the presence of a catalytic amount of indium trichloride is described. Benzylic alcohols, secondary alcohols, and tertiary alcohols were effectively reduced to give the corresponding alkanes in high yields. A compound bearing both primary and secondary hydroxyl groups was reduced only at the secondary site to afford the primary alcohol after workup with Bu4NF. This system showed high chemoselectivity only for the hydroxyl group while not reducing other functional groups that are readily reduced by standard reducing systems. Thus alcohols bearing ester, chloro, bromo, or nitro groups, which are sensitive to LiAlH4 or Zn/H+, were selectively reduced only at the hydroxyl sites by the chlorodiphenylsilane/InCl3 system. NMR studies revealed the reaction course. The hydrodiphenylsilyl ether is initially formed and then, with InCl3 acting as a Lewis acid, forms an oxonium. complex, which accelerates the desiloxylation with donation of the hydrogen to the carbon.