(Z)-O-methyl-4-methoxybenzohydroximoyl chloride | 57139-36-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (Z)-O-methyl-4-methoxybenzohydroximoyl chloride
• 英文别名: (1Z)-N,4-dimethoxybenzenecarboximidoyl chloride
• CAS: 57139-36-3
• 化学式: C₉H₁₀ClNO₂
• 分子量: 199.637
• InChiKey: PUOGATFISFCHML-LUAWRHEFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  30.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (Z)-O-methyl-4-methoxybenzohydroximoyl chloride 以 1,4-二氧六环 、 水 为溶剂， 生成 N-methoxy-4-methoxylbenzamide
  参考文献：
  名称：

  Mechanism of solvolysis reactions of O-methylbenzohydroximoyl halides. Stereoelectronic control in formation of and nucleophilic addition to nitrilium ions

  摘要：

  DOI：

  10.1021/jo01309a015
• 作为产物：
  描述：

  (E)-O-methyl-4-methoxybenzohydroximoyl chloride 在 盐酸 作用下， 以 1,4-二氧六环 为溶剂， 生成 (Z)-O-methyl-4-methoxybenzohydroximoyl chloride
  参考文献：
  名称：

  Mechanism of an acid-catalyzed geometric isomerization about a carbon-nitrogen double bond

  摘要：

  DOI：

  10.1021/jo00316a013

文献信息

• Mechanism of Methoxide Ion Substitution in the <i>Z</i> and <i>E</i> Isomers of <i>O</i>-Methylbenzohydroximoyl Halides
  作者：James E. Johnson、Debra D. Dolliver、Lonchun Yu、Diana C. Canseco、Michael A. McAllister、Jeffrey E. Rowe

  DOI：10.1021/jo030299e

  日期：2004.4.1

  isomers of O-methylbenzohydroximoyl halides [1Z and 1E, ArC(X)NOCH3] with sodium methoxide in 9:1 DMSO−methanol. The reactions of methoxide ion with hydroximoyl fluorides (X = F) are stereospecific. The reaction with 1Z (X = F) gives only the Z substitution product (1Z, X OCH3). The reaction of methoxide ion with 1E (X = F) is less selective, giving ca. 85% E substitution product. The Hammett ρ-values for

  在9：1 DMSO-甲醇中，对O-甲基苯并氧肟基卤化物的Z和E异构体[ 1Z和1E，ArC（X）NOCH 3 ]与甲醇钠的反应进行了动力学和立体化学研究。甲醇离子与羟肟基氟化物（X = F）的反应是立体定向的。与1Z（X = F）的反应仅给出Z取代产物（1Z，X OCH 3）。甲醇离子与1E（X = F）的反应选择性较低，大约为。E替代品占85％。的哈米特ρ值Z和E异构体（X = F）分别为+2.94和+3.30。1Z（Ar = C 6 H 5）的元素效应为2.21（X = Br）：1.00（X = Cl）：79.7（X = F）。所述1E元件效果（AR = C 6 H ^ 5）1.00（X = Cl）的：18.3（X = F）和（AR = 4-CH 3 OC 6 H ^ 4）1.97（X = Br的）：1.00（X = Cl）：12.1（X ＝ F）。激活用于这些反应的熵是否定的（例如，Δ小号⧧
• Mechanisms of Acid-Catalyzed <i>Z</i>/<i>E</i> Isomerization of Imines
  作者：James E. Johnson、Nora M. Morales、Andrea M. Gorczyca、Debra D. Dolliver、Michael A. McAllister

  DOI：10.1021/jo010067k

  日期：2001.11.1

  The kinetics and mechanism of acid-catalyzed Z/E isomerization of O-methylbenzohydroximoyl chloride (1Za and 1Ea), methyl O-methylbenzohydroximate (1Zb and 1Eb), ethyl O-methylbenzohydroximate (1Zc and 1Ec and five para and meta substituted derivatives), O-methylcinnamohydroximoyl chloride (2Za and 2Ea), and methyl O-methylcinnamohydroximate (2Zb and 2Zb) have been investigated. The kinetics of Z/E

  酸催化O-甲基苯并氢氧肟基氯（1Za和1Ea），O-甲基苯并氢肟酸甲酯（1Zb和1Eb），O-甲基苯并氢肟酸乙酯（1Zc和1Ec以及五种对位和间位取代的衍生物）的Z / E异构化动力学和机理，研究了O-甲基肉桂氢氧肟基氯（2Za和2Ea）和O-甲基肉桂氢氧肟酸甲酯（2Zb和2Zb）。这些亚胺的Z / E异构化动力学已在冰醋酸（1Ea和1Zc）和含HCl，三氟甲磺酸或四氟硼酸（1Ea，1Zb，2Ea和2Zb）的二恶烷溶液中进行了研究。异构化是通过（a）围绕质子化亚胺的碳-氮双键旋转（亚胺离子旋转）或（b）对质子化亚胺的亲核攻击形成四面体中间体而经历立体突变和亲核体损失（亲核催化）。羟肟基氯1Ea和2Ea仅通过亲核催化机理进行异构化。羟肟酸酯1Zb似乎能够通过任一机理异构化。羟肟酸酯2Zb可以仅通过亚胺离子旋转进行异构化。理论计算支持以下观念：质子化亚胺中的共轭增加会提高亚胺离子旋转的速率。氢
• Mechanism of amine and amide ion substitution reactions at the carbon-nitrogen double bond
  作者：James Elver Johnson、Abdolkarim Ghafouripour、Mohammad Arfan、Susan L. Todd、Deborah A. Sitz

  DOI：10.1021/jo00218a021

  日期：1985.9
• 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.
• Determination of configurations of N-methoxyimidoyl halides via catalytic hydrogenation. Synthesis of pure (E)-aldoximes
  作者：Takeshi Sakamoto、Kimio Okamoto、Yasuo Kikugawa

  DOI：10.1021/jo00037a053

  日期：1992.5