N-(benzoyloxy)-N-(benzyloxy)benzamide | 220168-39-8

• 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: N-(benzoyloxy)-N-(benzyloxy)benzamide
• 英文别名: benzyl N-(benzoyloxy)benzohydroxamate；N-benzoyloxy-N-benzyloxybenzamide；Benzamide, N-(benzoyloxy)-N-(phenylmethoxy)-；[benzoyl(phenylmethoxy)amino] benzoate
• CAS: 220168-39-8
• 化学式: C₂₁H₁₇NO₄
• 分子量: 347.37
• InChiKey: CWFVZMIGLFGLCL-UHFFFAOYSA-N

物化性质

• 沸点：
  475.8±38.0 °C(Predicted)
• 密度：
  1.251±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-(benzoyloxy)-N-(benzyloxy)benzamide 在 硫酸 作用下， 以 氘代乙腈 、 重水 为溶剂， 生成 苯甲酸 、 N-benzoyl-N-(benzyloxy)nitrenium ion
  参考文献：
  名称：

  A Comparison of the Reactivity and Mutagenicity of N-(Benzoyloxy)-N-(benzyloxy)benzamides

  摘要：

  A new series of N-(acyloxy)-N-alkoxybenzamides, N-(benzoyloxy) -N-(benzyloxy)benzamides 7 have been synthesized and have been found to be direct acting mutagens in Salmonella TA100. They undergo A(Al)1 solvolysis to give N-benzoyl-N-(benzyloxy)nitrenium ions 3 under conditions of acid catalysis as well as unusual B(Al)2 reactions at nitrogen with hydroxide. The latter process affords as intermediates the anomeric hydroxamic esters 4 which rearrange intramolecularly to esters in a HERON reaction. Rates of acid-catalyzed solvolysis and reaction with hydroxide ions correlate with Hammett a values with low sensitivity (rho = +0.32 and +0.55, respectively) in accordance with the A(Al)1 and B(Al)2 mechanisms. Mutagenicity for the series also appears to correlate with Hammett sigma values but with low, negative sensitivity (rho = -0.57), and their biological activity may be attributable to their stability under conditions of the Ames assay and hydrophobic binding to DNA, rather than their chemical reactivity.

  DOI：

  10.1021/jo980863z
• 作为产物：
  描述：

  N-(苯基甲氧基)苯甲酰胺 在 次氯酸叔丁酯 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 53.0h， 生成 N-(benzoyloxy)-N-(benzyloxy)benzamide
  参考文献：
  名称：

  A Comparison of the Reactivity and Mutagenicity of N-(Benzoyloxy)-N-(benzyloxy)benzamides

  摘要：

  A new series of N-(acyloxy)-N-alkoxybenzamides, N-(benzoyloxy) -N-(benzyloxy)benzamides 7 have been synthesized and have been found to be direct acting mutagens in Salmonella TA100. They undergo A(Al)1 solvolysis to give N-benzoyl-N-(benzyloxy)nitrenium ions 3 under conditions of acid catalysis as well as unusual B(Al)2 reactions at nitrogen with hydroxide. The latter process affords as intermediates the anomeric hydroxamic esters 4 which rearrange intramolecularly to esters in a HERON reaction. Rates of acid-catalyzed solvolysis and reaction with hydroxide ions correlate with Hammett a values with low sensitivity (rho = +0.32 and +0.55, respectively) in accordance with the A(Al)1 and B(Al)2 mechanisms. Mutagenicity for the series also appears to correlate with Hammett sigma values but with low, negative sensitivity (rho = -0.57), and their biological activity may be attributable to their stability under conditions of the Ames assay and hydrophobic binding to DNA, rather than their chemical reactivity.

  DOI：

  10.1021/jo980863z

文献信息

• Reaction of N-Acyloxy-N-alkoxyamides with Biological Thiol Groups
  作者：Stephen A. Glover、Meredith Adams

  DOI：10.1071/ch10470

  日期：——

  Mutagenic N-acyloxy-N-alkoxyamides 1 react with thiols by an SN2 process at nitrogen with displacement of carboxylate. They react with glutathione 4 in [D6]DMSO/D2O and methyl and ethyl esters of cysteine hydrochloride, 11 and 12, in [D4]methanol but the intermediate N-alkoxy-N-(alkylthio)amides undergo a rapid substitution reaction at sulfur by a second thiol molecule to give hydroxamic esters and disulfides. Arrhenius activation energies and entropies of activation obtained for a series of different N-benzyloxy-N-(4-substitutedbenzoyloxy)benzamides 13–17 were similar to those found for the SN2 reaction of the same series with N-methylaniline. Entropies of activation were strongly negative in keeping with polar separation and attendant solvation in the transition state, and in keeping with this, bimolecular reaction rate constants at 298 K correlated with Hammett σ constants with a positive ρ-value of 1.1. The structure of model N-methoxy-N-(methylthio)acetamide has been computed at the B3LYP/6–31G(d) level and exhibits properties atypical of other anomeric amides with more electronegative atoms at nitrogen. Relative to N,N-bisoxyl substitution, the combination of a sulfur and an oxygen atom at the amide nitrogen results in a relatively small reduction in amide resonance.

  致突变的 N-乙酰氧基-N-烷氧基酰胺 1 通过氮的 SN2 过程与硫醇发生反应，同时羧基发生位移。它们在[D6]DMSO/D2O 中与谷胱甘肽 4 反应，在[D4]甲醇中与半胱氨酸盐酸盐的甲酯和乙酯 11 和 12 反应，但中间的 N-烷氧基-N-（烷硫基）酰胺在硫处与第二个硫醇分子迅速发生取代反应，生成羟肟酯和二硫化物。一系列不同的 N-苄氧基-N-（4-取代苯甲酰氧基）苯甲酰胺 13-17 的阿伦尼乌斯活化能和活化熵与同一系列 N-甲基苯胺 SN2 反应的活化能和活化熵相似。活化熵为强负值，这与过渡态中的极性分离和随之而来的溶解有关；与此相一致，298 K 时的双分子反应速率常数与 Hammett σ 常数相关，正 ρ 值为 1.1。模型 N-甲氧基-N-(甲硫基)乙酰胺的结构是在 B3LYP/6-31G(d) 水平上计算得出的，其性质与氮原子电负性较强的其他同分异构体酰胺不同。与 N,N-二氧代相比，在酰胺氮上结合一个硫原子和一个氧原子会导致酰胺共振相对较小的减少。
• Campbell, John J.; Glover, Stephen A., Journal of Chemical Research, Miniprint, 1999, # 8, p. 2075 - 2096
  作者：Campbell, John J.、Glover, Stephen A.

  DOI：——

  日期：——
• A Comparison of the Reactivity and Mutagenicity of <i>N</i>-(Benzoyloxy)-<i>N</i>-(benzyloxy)benzamides
  作者：Stephen A. Glover、Gerard P. Hammond、Antonio M. Bonin

  DOI：10.1021/jo980863z

  日期：1998.12.1

  A new series of N-(acyloxy)-N-alkoxybenzamides, N-(benzoyloxy) -N-(benzyloxy)benzamides 7 have been synthesized and have been found to be direct acting mutagens in Salmonella TA100. They undergo A(Al)1 solvolysis to give N-benzoyl-N-(benzyloxy)nitrenium ions 3 under conditions of acid catalysis as well as unusual B(Al)2 reactions at nitrogen with hydroxide. The latter process affords as intermediates the anomeric hydroxamic esters 4 which rearrange intramolecularly to esters in a HERON reaction. Rates of acid-catalyzed solvolysis and reaction with hydroxide ions correlate with Hammett a values with low sensitivity (rho = +0.32 and +0.55, respectively) in accordance with the A(Al)1 and B(Al)2 mechanisms. Mutagenicity for the series also appears to correlate with Hammett sigma values but with low, negative sensitivity (rho = -0.57), and their biological activity may be attributable to their stability under conditions of the Ames assay and hydrophobic binding to DNA, rather than their chemical reactivity.