4-[(cyclohexyloxy)methyl]benzoic acid methyl ester | 1152517-74-2

• 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: 4-[(cyclohexyloxy)methyl]benzoic acid methyl ester
• 英文别名: methyl 4-(cyclohexyloxymethyl)benzoate
• CAS: 1152517-74-2
• 化学式: C₁₅H₂₀O₃
• 分子量: 248.322
• InChiKey: ULUSSKBGXNAFKJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (methoxymethoxy)cyclohexane 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 0.08h， 生成 4-[(cyclohexyloxy)methyl]benzoic acid methyl ester
  参考文献：
  名称：

  Expanded Substrate Scope and Improved Reactivity of Ether-Forming Cross-Coupling Reactions of Organotrifluoroborates and Acetals

  摘要：

  Mixed acetals and organotrifluoroborates undergo BF3 center dot OEt2-promoted cross-couplings to give dialkyl ethers under simple, mild conditions. A survey of reaction partners identified a hydroxamate leaving group that improves the regioselectivity and product yield in the BF3 center dot OEt2-promoted coupling reaction of mixed acetals and potassium alkynyl-, alkenyl-, aryl- and heteroaryltrifluoroborates to access substituted dialkyl ethers. This leaving group enables the reaction to proceed rapidly under mild conditions (0 degrees C, 5-60 min) and permits reactions with electron-deficient potassium aryltrifluoroborates that are less reactive with other acetal substrates. A study of the reaction mechanism and characterization of key intermediates by NMR spectroscopy and X-ray crystallography identified a role for the hydroxamate moiety as a reversible leaving group that serves to stabilize the key oxocarbenium intermediate and the need for a slight excess of organodifluoroborane to serve as a catalyst. A secondary role for the boron nucleophile as an activating ligand was also considered. These studies provide the basis for a general class of reagents that lead to dialkyl ethers by a simple, predictable cross-coupling reaction.

  DOI：

  10.1021/ja205174c

文献信息

• Synthesis of Ethers from Carbonyl Compounds by Reductive Etherification Catalyzed by Iron(III) and Silyl Chloride
  作者：Reko Leino、Risto Savela

  DOI：10.1055/s-0034-1380155

  日期：——

  with ethyl acetate as the solvent. A simple iron- and silyl chloride catalyzed method for the preparation of symmetrical and nonsymmetrical ethers is presented. Various aldehydes and ketones were reductively etherified by using triethylsilane as a reducing agent in the presence of 2 mol% of iron(III) oxo acetate and 8 mol% of chloro(trimethyl)silane. The reactions can be carried out at ambient temperatures

  摘要 提出了一种简单的铁和甲硅烷基氯催化的对称和非对称醚的制备方法。通过使用三乙基硅烷作为还原剂，在2摩尔％的乙酸铁（III）氧代乙酸酯和8摩尔％的氯（三甲基）硅烷的存在下，将各种醛和酮还原醚化。反应可以在环境温度和压力下以乙酸乙酯为溶剂进行。 提出了一种简单的铁和甲硅烷基氯催化的对称和非对称醚的制备方法。通过使用三乙基硅烷作为还原剂，在2摩尔％的乙酸铁（III）氧代乙酸酯和8摩尔％的氯（三甲基）硅烷的存在下，将各种醛和酮还原醚化。反应可以在环境温度和压力下以乙酸乙酯为溶剂进行。
• Expanded Substrate Scope and Improved Reactivity of Ether-Forming Cross-Coupling Reactions of Organotrifluoroborates and Acetals
  作者：Cam-Van T. Vo、T. Andrew Mitchell、Jeffrey W. Bode

  DOI：10.1021/ja205174c

  日期：2011.9.7

  Mixed acetals and organotrifluoroborates undergo BF3 center dot OEt2-promoted cross-couplings to give dialkyl ethers under simple, mild conditions. A survey of reaction partners identified a hydroxamate leaving group that improves the regioselectivity and product yield in the BF3 center dot OEt2-promoted coupling reaction of mixed acetals and potassium alkynyl-, alkenyl-, aryl- and heteroaryltrifluoroborates to access substituted dialkyl ethers. This leaving group enables the reaction to proceed rapidly under mild conditions (0 degrees C, 5-60 min) and permits reactions with electron-deficient potassium aryltrifluoroborates that are less reactive with other acetal substrates. A study of the reaction mechanism and characterization of key intermediates by NMR spectroscopy and X-ray crystallography identified a role for the hydroxamate moiety as a reversible leaving group that serves to stabilize the key oxocarbenium intermediate and the need for a slight excess of organodifluoroborane to serve as a catalyst. A secondary role for the boron nucleophile as an activating ligand was also considered. These studies provide the basis for a general class of reagents that lead to dialkyl ethers by a simple, predictable cross-coupling reaction.