Ethyl 4-chloro-3,3-dimethyl-2-oxobutanoate | 160194-01-4

• 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: Ethyl 4-chloro-3,3-dimethyl-2-oxobutanoate
• CAS: 160194-01-4
• 化学式: C₈H₁₃ClO₃
• 分子量: 192.642
• InChiKey: QCTOATRNRRFQCP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  Ethyl 4-chloro-3,3-dimethyl-2-oxobutanoate 在 四氯化钛 、 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 甲醇 、 乙醚 、 正戊烷 为溶剂， 反应 4.0h， 生成 Ethyl 2-(N-benzylamino)-4-chloro-3,3-dimethylbutanoate
  参考文献：
  名称：

  Synthesis of 1-Amino-2,2-dialkylcyclopropanecarboxylic Acids via Base-Induced Cyclization of .gamma.-Chloro-.alpha.-imino Esters

  摘要：

  beta-Chloro ketones were oxidatively transformed into alpha-keto carboxylic esters and condensed with primary amines in the presence of titanium(IV) chloride. Base-induced cyclization of the resulting gamma-chloro-alpha-imino esters, incorporating suitable N-substituents, led directly to 1-amino-2,2-dialkyl- cyclopropanecarboxylic ester derivatives via a 1,5-dehydrochlorination process. Syntheses of different N- and/or carboxyl-protected geminally (gem) dialkylated cyclopropane amino acids were developed, while access to the free alpha-amino acids is also given. The methodology used was further extended by reduction of the gamma-chloro-alpha-imino esters to functionalized gamma-chloro-alpha-amino esters,prior to ring closure, affording N-alkyl-gem-dialkyl-1-aminocyclopropanecarboxylic acid derivatives.

  DOI：

  10.1021/jo00102a022
• 作为产物：
  描述：

  1,1,4-Trichloro-1-(ethylthio)-3,3-dimethyl-2-butanone 在 对甲苯磺酸 、 silver carbonate 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 17.0h， 生成 Ethyl 4-chloro-3,3-dimethyl-2-oxobutanoate
  参考文献：
  名称：

  Synthesis of 1-Amino-2,2-dialkylcyclopropanecarboxylic Acids via Base-Induced Cyclization of .gamma.-Chloro-.alpha.-imino Esters

  摘要：

  beta-Chloro ketones were oxidatively transformed into alpha-keto carboxylic esters and condensed with primary amines in the presence of titanium(IV) chloride. Base-induced cyclization of the resulting gamma-chloro-alpha-imino esters, incorporating suitable N-substituents, led directly to 1-amino-2,2-dialkyl- cyclopropanecarboxylic ester derivatives via a 1,5-dehydrochlorination process. Syntheses of different N- and/or carboxyl-protected geminally (gem) dialkylated cyclopropane amino acids were developed, while access to the free alpha-amino acids is also given. The methodology used was further extended by reduction of the gamma-chloro-alpha-imino esters to functionalized gamma-chloro-alpha-amino esters,prior to ring closure, affording N-alkyl-gem-dialkyl-1-aminocyclopropanecarboxylic acid derivatives.

  DOI：

  10.1021/jo00102a022

文献信息

• Synthesis of 3,3-dimethylazetidine-2-carboxylic acid and some derivatives
  作者：Norbert De Kimpe、Marc Boeykens、Dirk Tourwé

  DOI：10.1016/s0040-4020(98)00024-6

  日期：1998.3

  for 1-(N-alkylamino)-2,2-dimethylcyclopropane-1-carboxylic esters via base-induced 1,3-dehydrochlorination, while the former substrates as transient species undergo 1,4-dehydrochlorination to the corresponding azetidines. The latter process was used for the synthesis of 3,3-dimethylazetidine-2-carboxylic acid, a new non-proteinogenic sterically hindered α-amino acid, via hydrogenolysis of methyl 1-benzyl-3

  γ-氯-α-（N-烷基亚氨基）酯在乙酸存在下被甲醇中的氰基硼氢化钠还原，并具有完全选择性，从而生成γ-氯-α-（N-烷基氨基）酯（在0°下反应） C）或1-烷基-3,3-二甲基氮杂环丁烷-2-羧酸酯（在回流下反应）。可分离的γ-氯-α-（N-烷基氨基）酯是通过碱诱导的1,3-脱氯化氢制备1-（N-烷基氨基）-2,2-二甲基环丙烷-1-羧酸酯的合适来源，而前者是底物因为瞬态物质经历1，4-脱氯化氢反应成相应的氮杂环丁烷。后一种方法通过甲基1-苄基-3,3-二甲基氮杂环丁烷-1-甲酸甲酯的氢解反应和3,3-二甲基氮杂环丁烷-2-羧酸的合成，这是一种新的非蛋白质位阻的α-氨基酸。随后进行酸性水解。
• Synthesis of 1-Amino-2,2-dialkylcyclopropanecarboxylic Acids via Base-Induced Cyclization of .gamma.-Chloro-.alpha.-imino Esters
  作者：Marc Boeykens、Norbert De Kimpe、Kourosch Abbaspour Tehrani

  DOI：10.1021/jo00102a022

  日期：1994.11

  beta-Chloro ketones were oxidatively transformed into alpha-keto carboxylic esters and condensed with primary amines in the presence of titanium(IV) chloride. Base-induced cyclization of the resulting gamma-chloro-alpha-imino esters, incorporating suitable N-substituents, led directly to 1-amino-2,2-dialkyl- cyclopropanecarboxylic ester derivatives via a 1,5-dehydrochlorination process. Syntheses of different N- and/or carboxyl-protected geminally (gem) dialkylated cyclopropane amino acids were developed, while access to the free alpha-amino acids is also given. The methodology used was further extended by reduction of the gamma-chloro-alpha-imino esters to functionalized gamma-chloro-alpha-amino esters,prior to ring closure, affording N-alkyl-gem-dialkyl-1-aminocyclopropanecarboxylic acid derivatives.