N-(4-chlorobenzyl)-N-nitrosoacetamide | 183156-72-1

• 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-(4-chlorobenzyl)-N-nitrosoacetamide
• 英文别名: N-[(4-chlorophenyl)methyl]-N-nitrosoacetamide
• CAS: 183156-72-1
• 化学式: C₉H₉ClN₂O₂
• 分子量: 212.636
• InChiKey: JGAQTKUCVYTPMH-UHFFFAOYSA-N

物化性质

• 沸点：
  309.0±44.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  49.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  甲苯 、 N-(4-chlorobenzyl)-N-nitrosoacetamide 、 苯 在 三氯化铝 作用下， 生成 4-氯二苯基甲烷 、 1-氯-4-(2-甲基苄基)苯
  参考文献：
  名称：

  反应性-选择性原理和芳香族化合物的亲电取代

  摘要：

  已使用N-亚硝酰胺分解作为亲电试剂的来源，对反应选择性原则（RSP）在Friedel-Crafts烷基化反应中的应用进行了重新研究。对于4-甲基苄基，苄基，4-氯苄基和4-硝基苄基阳离子，p f与σ +的关系图得出yield值分别为-3.4，-2.5，-2.4和-1.2。数据表明适用于芳族化合物的亲电取代的反应性-选择性原理与文献中的要求相反。关于弗里德-克拉夫茨苄基反应应发生反应性逆转的说法也有争议。

  DOI：

  10.1016/s0040-4039(97)10083-1
• 作为产物：
  描述：

  N-(4-氯苄基)乙酰胺 在 sodium acetate 、 dinitrogen tetraoxide 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以100%的产率得到N-(4-chlorobenzyl)-N-nitrosoacetamide
  参考文献：
  名称：

  A Study of Essentially Free Carbocations Derived via Diazonium and Oxo Diazonium Ions in the Liquid Phase

  摘要：

  Nitrogen- and nitrous oxide-separated ion pairs containing Li-substituted benzyl cations and carboxylate or tosylate anions were prepared by thermolysis of N-nitroso- and N-nitroamides, acidification of phenyldiazomethane, and nitrosation of N-benzyl-O-benzoylhydroxylamine. The cations were generated in benzene/toluene and benzene/anisole mixtures and were found to partition between the counterion and the solvent and between the aromatic cosolvent and benzene. A familial relationship among the methods was observed. As the cation became more reactive, the yield of solvent-derived products (SDPs) rose and the ratio of rate constants for its reaction with toluene versus benzene, k(T)/k(B), fell. The yield of SDP also rose as the temperature was decreased and as N-2 was replaced by N2O; however, k(T)/k(B) remained unchanged. Inert diluents had no effect on k(T)/k(B) but decreased hydrocarbon yield by 40% on 2-fold dilution. In the presence of reactive diluents that are converted into secondary alkylating agents, both the % hydrodarbon and k(T)/k(B) rose. These results are interpreted in terms of the intermediacy of inert-molecule-separated ion pairs (IMSIPs) in deamination. The cation reacted with benzoates and tosylates not only at the oxygens but also at the ipso carbon; subsequent decarboxylation and desulfonylation, respectively, led to diphenylmethanes. The ester/SDP ratio is introduced as a new measure of carbocation reactivity.

  DOI：

  10.1021/jo990494m

文献信息

• A Study of <i>N</i>-Nitrosoamide-Mediated Friedel−Crafts Type Benzylation of Benzene−Toluene and Benzene−Anisole¹^a
  作者：Ron W. Darbeau、Emil H. White

  DOI：10.1021/jo9916378

  日期：2000.2.1

  deuterium rearrangements (or coupled benzyl rearrangements) in the arenium ion intermediate. Kinetic isotope effects were not detected. The methyl substituent on toluene appears to affect intermolecular selectivity (k(T)/k(B)) and intramolecular selectivity (o, m, p distribution) to similar degrees. A mechanism is proposed in which both selectivities are determined by activation energy differences in

  氮分离的碳阳离子-羧酸根离子对被用作芳族化合物烷基化反应中碳阳离子的来源。N-亚硝基酰胺用于这些氮分子分离的离子对是研究烷基化的标准酸催化Friedel-Crafts方法的极佳替代品，因为它具有以下变量：亲电试剂的高反应活性，产物的稳定性，严格的动力学控制，均质性，没有过度烷基化，化学反应简单以及良好的产品平衡。在苯-甲苯和苯甲醚-苯混合物的脱氨苄基反应中，k（X）/ k（B）和％间位异构体的值与标准苄基化反应中观察到的值显着不同，这表明脱氨基亲电体比标准Friedel-Crafts方法生成的亲电性更高。反应显示分子间和分子内选择性之间成正比，因此遵循布朗选择性关系（BSR）。2,4,6-三甲苯基甲苯的苄基化未提供任何证据表明在芳族离子中间体中发生氘重排（或偶合的苄基重排）。未检测到动力学同位素效应。甲苯上的甲基取代基似乎以相似的程度影响分子间选择性（k（T）/ k（B））和分子内选择性（
• A New Look at the Friedel−Crafts Alkylation Reaction¹
  作者：Emil H. White、Ron W. Darbeau、Yulong Chen、Steven Chen、David Chen

  DOI：10.1021/jo960935r

  日期：1996.11.15
• The Reactivity-Selectivity principle and the electrophilic substitution of aromatic compounds
  作者：Emil H. White

  DOI：10.1016/s0040-4039(97)10083-1

  日期：1997.11

  application of the Reactivity-Selectivity principle (RSP) to the Friedel-Crafts alkylation reaction has been reinvestigated using the N-nitrosoamide decomposition as the source of electrophiles. Plots of pfvsσ+ for 4-methylbenzyl, benzyl, 4-chlorobenzyl, and 4-nitrobenzyl cations] yielded ϱ values of −3.4, −2.5, −2.4, and −1.2, resp. The data indicate that the Reactivity-Selectivity Principle applicable

  已使用N-亚硝酰胺分解作为亲电试剂的来源，对反应选择性原则（RSP）在Friedel-Crafts烷基化反应中的应用进行了重新研究。对于4-甲基苄基，苄基，4-氯苄基和4-硝基苄基阳离子，p f与σ +的关系图得出yield值分别为-3.4，-2.5，-2.4和-1.2。数据表明适用于芳族化合物的亲电取代的反应性-选择性原理与文献中的要求相反。关于弗里德-克拉夫茨苄基反应应发生反应性逆转的说法也有争议。
• A Study of Essentially Free Carbocations Derived via Diazonium and Oxo Diazonium Ions in the Liquid Phase
  作者：Ron W. Darbeau、Emil H. White、Fenhong Song、Nyla R. Darbeau、James Chou

  DOI：10.1021/jo990494m

  日期：1999.8.1

  Nitrogen- and nitrous oxide-separated ion pairs containing Li-substituted benzyl cations and carboxylate or tosylate anions were prepared by thermolysis of N-nitroso- and N-nitroamides, acidification of phenyldiazomethane, and nitrosation of N-benzyl-O-benzoylhydroxylamine. The cations were generated in benzene/toluene and benzene/anisole mixtures and were found to partition between the counterion and the solvent and between the aromatic cosolvent and benzene. A familial relationship among the methods was observed. As the cation became more reactive, the yield of solvent-derived products (SDPs) rose and the ratio of rate constants for its reaction with toluene versus benzene, k(T)/k(B), fell. The yield of SDP also rose as the temperature was decreased and as N-2 was replaced by N2O; however, k(T)/k(B) remained unchanged. Inert diluents had no effect on k(T)/k(B) but decreased hydrocarbon yield by 40% on 2-fold dilution. In the presence of reactive diluents that are converted into secondary alkylating agents, both the % hydrodarbon and k(T)/k(B) rose. These results are interpreted in terms of the intermediacy of inert-molecule-separated ion pairs (IMSIPs) in deamination. The cation reacted with benzoates and tosylates not only at the oxygens but also at the ipso carbon; subsequent decarboxylation and desulfonylation, respectively, led to diphenylmethanes. The ester/SDP ratio is introduced as a new measure of carbocation reactivity.