(E)-O-methyl-phenylbenzohydroximoyl chloride | 173171-14-7

• 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: (E)-O-methyl-phenylbenzohydroximoyl chloride
• 英文别名: (1E)-N-methoxy-4-phenylbenzenecarboximidoyl chloride
• CAS: 173171-14-7
• 化学式: C₁₄H₁₂ClNO
• 分子量: 245.708
• InChiKey: NPTHSXKWTQRUEL-JQIJEIRASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  N-methoxy-[1,1'-biphenyl]-4-carboxamide 在 五氯化磷 作用下， 以 四氯化碳 、 苯 为溶剂， 反应 30.0h， 生成 (E)-O-methyl-phenylbenzohydroximoyl chloride
  参考文献：
  名称：

  Mechanism of Hydrolysis of (Z)- and (E)-O-Methylbenzohydroximoyl Chloride

  摘要：

  The first-order rate constants for the hydrolysis (1:3 dioxane-water, pH=7) of (E)-O-methylbenzohydroximoyl chloride [C6H5C(Cl)=NOCH3, 1Ea] and several 4-substituted derivatives have been measured. A Hammett plot of these rate constants vs sigma(+) gave a rho value of -1.4. Molecular orbital calculations (AM1) have been carried out on (Z)-O-methylbenzohydroximoyl chloride (1Za), a hydrazonyl chloride [C6H5C(Cl)=NNHCH3], and the corresponding nitrilium ions [C6H5C=NOCH3+ and C6H5C=NNHCH3+] in an attempt to gain insight into the differences in the reactivities of these two systems. A study of the effect of solvent composition on the rates of hydrolysis of(Z)-and (E)-O-methyl-4-methoxybenzohydroximoyl chloride (1Zb and 1Eb) has been carried out using dioxane/water solutions of various compositions. The Grunwald-Winstein m values were determined to be 1.1 and 0.95 for the Z and E isomers, respectively. The activation parameters for the hydrolysis of 1Zb and 1Eb are as follows: Delta H double dagger = 34 kcal/mol and Delta S double dagger = +2 eu (1Zb) and Delta H double dagger = 40 kcal/mol and Delta S double dagger = +8 eu (1Eb). When plots of ln k/T vs 1/T were extrapolated to 25 degrees C, a rate constant ratio for k(1Zb)/k(1Eb) of about 10(5) was obtained. It is concluded that both (Z)- and (E)-hydroximoyl chlorides undergo hydrolysis by rate-limiting ionization to a nitrilium ion (ArC=NOCH3+). The large difference in ionization rates for 1Zb and 1Eb is attributed to a stereoelectronic effect.

  DOI：

  10.1021/jo950938o

文献信息

• Mechanism of Hydrolysis of (<i>Z</i>)- and (<i>E</i>)-<i>O</i>-Methylbenzohydroximoyl Chloride
  作者：James E. Johnson、Elvira C. Riesgo、Issam Jano

  DOI：10.1021/jo950938o

  日期：1996.1.1

  The first-order rate constants for the hydrolysis (1:3 dioxane-water, pH=7) of (E)-O-methylbenzohydroximoyl chloride [C6H5C(Cl)=NOCH3, 1Ea] and several 4-substituted derivatives have been measured. A Hammett plot of these rate constants vs sigma(+) gave a rho value of -1.4. Molecular orbital calculations (AM1) have been carried out on (Z)-O-methylbenzohydroximoyl chloride (1Za), a hydrazonyl chloride [C6H5C(Cl)=NNHCH3], and the corresponding nitrilium ions [C6H5C=NOCH3+ and C6H5C=NNHCH3+] in an attempt to gain insight into the differences in the reactivities of these two systems. A study of the effect of solvent composition on the rates of hydrolysis of(Z)-and (E)-O-methyl-4-methoxybenzohydroximoyl chloride (1Zb and 1Eb) has been carried out using dioxane/water solutions of various compositions. The Grunwald-Winstein m values were determined to be 1.1 and 0.95 for the Z and E isomers, respectively. The activation parameters for the hydrolysis of 1Zb and 1Eb are as follows: Delta H double dagger = 34 kcal/mol and Delta S double dagger = +2 eu (1Zb) and Delta H double dagger = 40 kcal/mol and Delta S double dagger = +8 eu (1Eb). When plots of ln k/T vs 1/T were extrapolated to 25 degrees C, a rate constant ratio for k(1Zb)/k(1Eb) of about 10(5) was obtained. It is concluded that both (Z)- and (E)-hydroximoyl chlorides undergo hydrolysis by rate-limiting ionization to a nitrilium ion (ArC=NOCH3+). The large difference in ionization rates for 1Zb and 1Eb is attributed to a stereoelectronic effect.