3-hexene-2-acetate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-hexene-2-acetate
• 英文别名: Hex-3-en-2-yl acetate
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: IUARUSFAOMRIPR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (E)-4-hexen-3-yl acetate 在 CoCl₂ 作用下， 以 乙腈 为溶剂， 生成 3-hexene-2-acetate
  参考文献：
  名称：

  Cobalt(II)-Catalyzed Conversion of Allylic Alcohols/Acetates to Allylic Amides in the Presence of Nitriles

  摘要：

  Various secondary allylic alcohols or their acetates and tertiary allylic alcohols can be converted to the corresponding transposed allylic amides in the presence of a catalytic quantity of cobalt(II) chloride and acetic anhydride in acetonitrile. Tertiary alcohols undergo complete rearrangement whereas secondary ones afford a mixture of regioisomers. Moderate yields of amides are also obtained by reacting acrylonitrile with secondary alcohols in 1,2-dichloroethane. The presence of acetic anhydride or acetic acid is crucial to the formation of amides as the absence of the former affords no amides and the allylic alcohols are mainly recovered as regioisomeric mixtures. The regioselectivity during amide formation can be enhanced by using cobalt complexes 14-16 in acetic acid medium. Some preliminary studies indicate that these reactions are proceeding via an pi-allyl complex or tight ion pair rather than a [3,3] sigmatropic rearrangement of acetamidate obtained in a Pinner reaction.

  DOI：

  10.1021/jo00114a013

文献信息

• PROCESS FOR PRODUCING ESTER COMPOUND HAVING a,ß-UNSATURATED BOND
  申请人：Kaneda Kiyotomi

  公开号：US20120316360A1

  公开（公告）日：2012-12-13

  A process for producing an α,β-unsaturated bond-containing ester compound, comprising: reacting an internal olefin or a cyclic olefin having one carbon-carbon double bond or more at a position other than terminals of a molecule thereof (the internal olefin and the cyclic olefin may each contain a hetero atom) with a carboxylic acid in an amide-based solvent in the presence of a palladium catalyst, a base, and molecular oxygen, thereby bonding a carboxyl group of the carboxylic acid to at least one of carbon atoms constituting the carbon-carbon double bond and carbon atoms at allylic positions of the internal olefin or the cyclic olefin, to obtain an ester compound having an α,β-unsaturated bond, the amide-based solvent being represented by the following formula (1): (in the formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms; R 2 and R 3 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group; and when R 1 and R 2 are alkyl groups, R 1 and R 2 may be bonded to each other to form a ring structure).

  一种生产α，β-不饱和键含量酯化合物的方法，包括：在存在钯催化剂、碱和分子氧的情况下，将具有一个或多个碳-碳双键的内部烯烃或环烯烃（该内部烯烃和环烯烃可能含有杂原子）与羧酸在酰胺基溶剂中反应，从而将羧基与内部烯烃或环烯烃的烯烃碳原子中至少一个或烯丙位碳原子中的至少一个之一结合，以获得具有α，β-不饱和键的酯化合物，所述酰胺基溶剂由以下式（1）表示：（在式（1）中，R1代表具有1至4个碳原子的烷基基团；R2和R3各自独立地代表具有1至4个碳原子的烷基基团或芳基；当R1和R2为烷基基团时，R1和R2可以结合在一起形成环结构）。
• Cobalt(II)-Catalyzed Conversion of Allylic Alcohols/Acetates to Allylic Amides in the Presence of Nitriles
  作者：Manoj Mukhopadhyay、M. Madhava Reddy、G. C. Maikap、Javed Iqbal

  DOI：10.1021/jo00114a013

  日期：1995.5

  Various secondary allylic alcohols or their acetates and tertiary allylic alcohols can be converted to the corresponding transposed allylic amides in the presence of a catalytic quantity of cobalt(II) chloride and acetic anhydride in acetonitrile. Tertiary alcohols undergo complete rearrangement whereas secondary ones afford a mixture of regioisomers. Moderate yields of amides are also obtained by reacting acrylonitrile with secondary alcohols in 1,2-dichloroethane. The presence of acetic anhydride or acetic acid is crucial to the formation of amides as the absence of the former affords no amides and the allylic alcohols are mainly recovered as regioisomeric mixtures. The regioselectivity during amide formation can be enhanced by using cobalt complexes 14-16 in acetic acid medium. Some preliminary studies indicate that these reactions are proceeding via an pi-allyl complex or tight ion pair rather than a [3,3] sigmatropic rearrangement of acetamidate obtained in a Pinner reaction.