Azetidin-1-yl-phenyl-methanone O-methyl-oxime | 142701-87-9

• 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: Azetidin-1-yl-phenyl-methanone O-methyl-oxime
• 英文别名: (E)-1-(azetidin-1-yl)-N-methoxy-1-phenylmethanimine
• CAS: 142701-87-9
• 化学式: C₁₁H₁₄N₂O
• 分子量: 190.245
• InChiKey: AVINUIXRPOTHNL-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  24.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  Azetidin-1-yl-phenyl-methanone O-methyl-oxime 以 二苯醚 为溶剂， 反应 10.0h， 以29%的产率得到Azetidin-1-yl-phenyl-methanone O-methyl-oxime
  参考文献：
  名称：

  Mechanisms and stereochemistry of amine substitution reactions at the carbon-nitrogen double bond

  摘要：

  The reaction of (Z)-O-methyl-p-nitrobenzohydroximoyl chloride [4-NO2C6H4C(Cl)=NOCH3] with morpholine, piperidine, pyrrolidine, and azetidine gives the corresponding (Z)-amidoximes [4-NO2C6H4C(NR1R2)=NOCH3]. The rate equations for these reactions in benzene solution contain both first-order and second-order terms in amine. The rates of these reactions increase with increasing basicity [k(pyrrolidine > k(morpholine)] and d size of the amine [k(azetidine) > k(pyrrolidine) > k(piperidine)]. The approximate Hammett rho-values for the reaction of (Z)-hydroximoyl chlorides with azetidine are +1.0 for the amine-catalyzed process and 0 for the uncatalyzed pathway. The element effect, k(p-nitrobenzohydroximoyl bromide)/k(p-nitrobenzohydroximoyl chloride), is 11.9 for the amine-catalyzed reaction and 8.16 for the uncatalyzed reaction. These results suggest that the reactions proceed by an addition-elimination mechanism (A(N) + D(N)) in which the amine is deprotonating the zwitterionic tetrahedral intermediate in the amine-catalyzed process. The slow reaction of azetidine in benzene solution with (E)-O-methyl-p-nitrobenzohydroximoyl chloride gives a mixture of the (Z)- and (E)-amidoxime with the E isomer predominating (E/Z is-approximately-equal-to 98:2). The rate equation for this reaction contains first-order and third-order terms in azetidine. It is suggested that the amine-catalyzed route involves nucleophilic attack by an amine monomer to form a tetrahedral intermediate which breaks down with the assistance of an amine dimer (or the homoconjugate acid of the amine). The difference in the observed rate equations for (Z)- and (E)-hydroximoyl chlorides with azetidine is attributed to stereoelectronic effects.

  DOI：

  10.1021/jo00043a022

文献信息

• Mechanisms and stereochemistry of amine substitution reactions at the carbon-nitrogen double bond
  作者：James Elver Johnson、Susan L. Todd、Susan M. Dutson、Abdolkarim Ghafouripour、Reidun M. Alderman、Martha R. Hotema

  DOI：10.1021/jo00043a022

  日期：1992.8

  The reaction of (Z)-O-methyl-p-nitrobenzohydroximoyl chloride [4-NO2C6H4C(Cl)=NOCH3] with morpholine, piperidine, pyrrolidine, and azetidine gives the corresponding (Z)-amidoximes [4-NO2C6H4C(NR1R2)=NOCH3]. The rate equations for these reactions in benzene solution contain both first-order and second-order terms in amine. The rates of these reactions increase with increasing basicity [k(pyrrolidine > k(morpholine)] and d size of the amine [k(azetidine) > k(pyrrolidine) > k(piperidine)]. The approximate Hammett rho-values for the reaction of (Z)-hydroximoyl chlorides with azetidine are +1.0 for the amine-catalyzed process and 0 for the uncatalyzed pathway. The element effect, k(p-nitrobenzohydroximoyl bromide)/k(p-nitrobenzohydroximoyl chloride), is 11.9 for the amine-catalyzed reaction and 8.16 for the uncatalyzed reaction. These results suggest that the reactions proceed by an addition-elimination mechanism (A(N) + D(N)) in which the amine is deprotonating the zwitterionic tetrahedral intermediate in the amine-catalyzed process. The slow reaction of azetidine in benzene solution with (E)-O-methyl-p-nitrobenzohydroximoyl chloride gives a mixture of the (Z)- and (E)-amidoxime with the E isomer predominating (E/Z is-approximately-equal-to 98:2). The rate equation for this reaction contains first-order and third-order terms in azetidine. It is suggested that the amine-catalyzed route involves nucleophilic attack by an amine monomer to form a tetrahedral intermediate which breaks down with the assistance of an amine dimer (or the homoconjugate acid of the amine). The difference in the observed rate equations for (Z)- and (E)-hydroximoyl chlorides with azetidine is attributed to stereoelectronic effects.