Azetidin-1-yl-(4-chloro-phenyl)-methanone O-methyl-oxime | 142701-90-4

• 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-(4-chloro-phenyl)-methanone O-methyl-oxime
• 英文别名: (Z)-1-(azetidin-1-yl)-1-(4-chlorophenyl)-N-methoxymethanimine
• CAS: 142701-90-4
• 化学式: C₁₁H₁₃ClN₂O
• 分子量: 224.69
• InChiKey: ZCEHEXDWBWOSQC-QBFSEMIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 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

• 作为反应物：
  描述：

  Azetidin-1-yl-(4-chloro-phenyl)-methanone O-methyl-oxime 以 二苯醚 为溶剂， 反应 10.0h， 以33%的产率得到Azetidin-1-yl-(4-chloro-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
• 作为产物：
  描述：

  杂氮环丁烷 、 (Z)-O-methyl-p-chlorobenzohydroximoyl chloride 以 乙腈 为溶剂， 生成 Azetidin-1-yl-(4-chloro-phenyl)-methanone O-methyl-oxime
  参考文献：
  名称：

  乙腈溶液中羟肟基卤化物与胺的双分子取代反应机理

  摘要：

  （Z）-O-甲基苯并氢氧氯化物[ArC（Cl）NOCH 3 ]在乙腈溶液中与吗啉，吡咯烷和氮杂环丁烷反应，得到相应的（Z）-氨基肟[ArC（NR 1 R 2）NOCH 3 ]在乙腈中的反应。这些反应的速率是在拟一级条件（过量胺）下测量的。发现反应遵循总体二级动力学（在胺中一级）。与吡咯烷反应的哈米特ρ值（带有σ）为+ 0·92。对硝基化合物与吡咯烷的反应产生了显着的元素效应[ k（p-硝基苯甲氧基肟基溴化物/ k（p）-硝基苯甲氧基肟基氯＝ 10]。从吗啉和哌啶与对-硝基羟肟基氯的反应估计布朗斯通的β值为0·38 。（E）-O-甲基-对硝基苯并氧肟基氯与氮杂环丁烷的较慢反应主要产生（E）-ami胺肟（E：Z≈98：2）此反应也遵循二级动力学。将该研究中的动力学观察结果与在苯溶液中早期工作中获得的相应结果进行比较。建议在乙腈溶液中，反应通过加成消除机理进行，该速率决定氯离子的损失速率（A N

  DOI：

  10.1002/poc.610080505

文献信息

• Mechanism of bimolecular substitution reactions of hydroximoyl halides with amines in actonitrile solution
  作者：James E. Johnson、Susan M. Dutson、Debra D. Dolliver、Susan L. Todd、Martha Hotema

  DOI：10.1002/poc.610080505

  日期：1995.5

  ρ-value (with σ) for the reaction with pyrrolidine is +0·92. The reaction of the p-nitro compound with pyrrolidine gives a significant element effect [k(p-nitrobenzohydroximoyl bromide)/k(p)-nitrobenzohydroximoyl chloride = 10]. A Brϕonsted β-value of 0·38 was estimated from the reactions of morpholine and piperidine with the p-nitrohydroximoyl chloride. The slower reaction of (E)-O-methyl-p-nitrobenzohydroximoyl

  （Z）-O-甲基苯并氢氧氯化物[ArC（Cl）NOCH 3 ]在乙腈溶液中与吗啉，吡咯烷和氮杂环丁烷反应，得到相应的（Z）-氨基肟[ArC（NR 1 R 2）NOCH 3 ]在乙腈中的反应。这些反应的速率是在拟一级条件（过量胺）下测量的。发现反应遵循总体二级动力学（在胺中一级）。与吡咯烷反应的哈米特ρ值（带有σ）为+ 0·92。对硝基化合物与吡咯烷的反应产生了显着的元素效应[ k（p-硝基苯甲氧基肟基溴化物/ k（p）-硝基苯甲氧基肟基氯＝ 10]。从吗啉和哌啶与对-硝基羟肟基氯的反应估计布朗斯通的β值为0·38 。（E）-O-甲基-对硝基苯并氧肟基氯与氮杂环丁烷的较慢反应主要产生（E）-ami胺肟（E：Z≈98：2）此反应也遵循二级动力学。将该研究中的动力学观察结果与在苯溶液中早期工作中获得的相应结果进行比较。建议在乙腈溶液中，反应通过加成消除机理进行，该速率决定氯离子的损失速率（A N
• 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.