2-chloroethyl 2-oxo-2-phenylacetate | 22964-15-4

• 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: 2-chloroethyl 2-oxo-2-phenylacetate
• 英文别名: 2-chloroethyl2-oxo-2-phenylacetate；2-Chlorethyl-phenylglyoxylat
• CAS: 22964-15-4
• 化学式: C₁₀H₉ClO₃
• 分子量: 212.633
• InChiKey: HXEWPRCEKAHMHV-UHFFFAOYSA-N

物化性质

• 沸点：
  307.1±25.0 °C(Predicted)
• 密度：
  1.259±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-chloroethyl 2-oxo-2-phenylacetate 以 苯 为溶剂， 生成 氯乙醛 、 苯甲醛 、 Oxo-phenyl-acetic acid vinyl ester 、 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  Photochemical Reactions of Halo-/Aryl Sulfide-Substituted Alkyl Phenylglyoxylate, an Assessment of the Lifetime of the Intermediate 1,4-Biradical

  摘要：

  Photochemical reactions of several halo/aryl sulfide-substituted alkyl phenylglyoxylates (1) were studied. For 2'-bromo-(Ib), 2'-iodo- (1c), 2'-(phenylthio)- (1d), and 2'-(phenylsulfinyl)- (1e) ethyl phenylglyoxylate, vinyl phenylglyoxylate (2), proposed to be the result of beta-elimination from the 1,4-biradical formed by triplet state gamma-hydrogen abstraction, is the dominant photoproduct. In the cases Ib and Id Norrish Type II products were also observed. Vinyl phenylglyoxylate (2) was not observed with 2'-chloroethyl (la), 3'-bromopropyl (If), and 3'-(phenylthio)propyl (1g) phenylglyoxylate. The lifetime of the 1,4-biradical intermediate is deduced from the competition between the beta-elimination of the monoradical and the normal biradical decay. The triplet lifetime and the photoreaction efficiency of 1 were not significantly affected by halogen-substitution.

  DOI：

  10.1021/jo971201x
• 作为产物：
  描述：

  苯乙醛酸钾盐 在 四丁基溴化铵 作用下， 以 二甲基亚砜 、 1,2-二氯乙烷 为溶剂， 反应 8.5h， 生成 2-chloroethyl 2-oxo-2-phenylacetate
  参考文献：
  名称：

  中性条件下α-氧代羧酸酯与α-溴代酮的无过渡金属形式脱羧偶联：简单地获得1,3-二酮

  摘要：

  提出了α-氧代羧酸盐和α-溴代酮之间无过渡金属的正式脱羧偶联反应，以合成1,3-二酮衍生物。在该反应中，可以使用广泛的底物，并且不需要金属基试剂或额外的碱。DFT计算表明，该反应通过偶联反应继之以脱羧机理进行，α-溴酮在中性条件下前所未有地充当亲核试剂。决定速率的步骤是通过热分解形成的异常氢键结合的烯醇化物。

  DOI：

  10.1002/anie.201409361

文献信息

• Copper-catalyzed coupling of anthranils and α-keto acids: direct synthesis of α-ketoamides
  作者：Ping-Gui Li、Hao Zhu、Min Fan、Cheng Yan、Kai Shi、Xi-Wen Chi、Liang-Hua Zou

  DOI：10.1039/c9ob00822e

  日期：——

  Copper-catalyzed coupling of α-keto acids with anthranils is reported for the synthesis of α-ketoamides. This process involves N-O/C-O bond cleavages and C-N bond formation. Furthermore, the decarboxylation of α-keto acids can be successfully suppressed under redox-neutral conditions.

  铜催化的α-酮酸与蒽的偶联被报道用于α-酮酰胺的合成。该过程涉及NO / CO键的裂解和CN键的形成。此外，在氧化还原中性条件下可以成功抑制α-酮酸的脱羧。
• Photochemical Reactions of Halo-/Aryl Sulfide-Substituted Alkyl Phenylglyoxylate, an Assessment of the Lifetime of the Intermediate 1,4-Biradical
  作者：Shengkui Hu、Douglas C. Neckers

  DOI：10.1021/jo971201x

  日期：1997.10.1

  Photochemical reactions of several halo/aryl sulfide-substituted alkyl phenylglyoxylates (1) were studied. For 2'-bromo-(Ib), 2'-iodo- (1c), 2'-(phenylthio)- (1d), and 2'-(phenylsulfinyl)- (1e) ethyl phenylglyoxylate, vinyl phenylglyoxylate (2), proposed to be the result of beta-elimination from the 1,4-biradical formed by triplet state gamma-hydrogen abstraction, is the dominant photoproduct. In the cases Ib and Id Norrish Type II products were also observed. Vinyl phenylglyoxylate (2) was not observed with 2'-chloroethyl (la), 3'-bromopropyl (If), and 3'-(phenylthio)propyl (1g) phenylglyoxylate. The lifetime of the 1,4-biradical intermediate is deduced from the competition between the beta-elimination of the monoradical and the normal biradical decay. The triplet lifetime and the photoreaction efficiency of 1 were not significantly affected by halogen-substitution.
• Transition-Metal-Free Formal Decarboxylative Coupling of α-Oxocarboxylates with α-Bromoketones under Neutral Conditions: A Simple Access to 1,3-Diketones
  作者：Zhen He、Xiaotian Qi、Shiqing Li、Yinsong Zhao、Ge Gao、Yu Lan、Yiwei Wu、Jingbo Lan、Jingsong You

  DOI：10.1002/anie.201409361

  日期：2015.1.12

  A transition‐metal‐free formal decarboxylative coupling reaction between α‐oxocarboxylates and α‐bromoketones to synthesize 1,3‐diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal‐based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism

  提出了α-氧代羧酸盐和α-溴代酮之间无过渡金属的正式脱羧偶联反应，以合成1,3-二酮衍生物。在该反应中，可以使用广泛的底物，并且不需要金属基试剂或额外的碱。DFT计算表明，该反应通过偶联反应继之以脱羧机理进行，α-溴酮在中性条件下前所未有地充当亲核试剂。决定速率的步骤是通过热分解形成的异常氢键结合的烯醇化物。