1,1-dibromo-4-chloro-3,3-dimethyl-2-butanone | 146446-29-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1-dibromo-4-chloro-3,3-dimethyl-2-butanone
• 英文别名: InChI=1/C6H9Br2ClO/c1-6(2,3-9)4(10)5(7)8/h5H,3H2,1-2H；1,1-dibromo-4-chloro-3,3-dimethylbutan-2-one
• CAS: 146446-29-9
• 化学式: C₆H₉Br₂ClO
• 分子量: 292.398
• InChiKey: GNCANKHOJREUSW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  1,1-dibromo-4-chloro-3,3-dimethyl-2-butanone 在 磺酰氯 、 sodium methylate 、 silver carbonate 作用下， 反应 18.08h， 生成 4-Chloro-1,1,1-trimethoxy-3,3-dimethyl-2-butanone
  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：

  2,2-Dimethyl-3-oxo-1-butyl trifluoroacetate 在 吡啶 、 溴 、 碳酸氢钠 、 lithium chloride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 64.0h， 生成 1,1-dibromo-4-chloro-3,3-dimethyl-2-butanone
  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

• Selective transformation of α,α-dibromomethyl ketones into α-monosulfenylated ketones
  作者：Marc Boeykens、Norbert De Kimpe

  DOI：10.1016/s0040-4020(01)89544-2

  日期：1994.1

  When α,α-dibromomethyl ketones are treated with sodium thiolates only the α-monosulfenylated ketones are formed. Evidence is put forward that the reaction mechanism proceeds by an initial nucleophilic substitution of one bromo atom and reduction by single electron transfer (SET) - hydrogen atom abstraction of the second bromo atom.

  当用硫醇钠处理α，α-二溴甲基酮时，仅形成α-单亚磺酰基化的酮。提出的证据表明，反应机理是通过一个溴原子的初始亲核取代并通过单电子转移（SET）-第二个溴原子的氢原子抽象而还原而进行的。
• 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.

表征谱图