3-(N-Phenylhydroxyamino)-2-methylhex-1-ene

• 分子结构分类: 有机化合物 - 苯类化合物 - N-苯基羟胺
• 英文名称: 3-(N-Phenylhydroxyamino)-2-methylhex-1-ene
• 英文别名: N-(2-methylhex-1-en-3-yl)-N-phenylhydroxylamine
• 化学式: C₁₃H₁₉NO
• 分子量: 205.3
• InChiKey: OGJKHZMHCAUZJQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  23.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-甲基-2-己烯 、 亚硝基苯 以 1,4-二氧六环 为溶剂， 反应 2.5h， 以25%的产率得到3-(N-Phenylhydroxyamino)-2-methylhex-1-ene
  参考文献：
  名称：

  Mechanistic Aspects of Molybdenum-Promoted Allylic Amination

  摘要：

  The mechanism of molybdenum-mediated allylic amination by phenylhydroxylamine has been probed through a variety of kinetics, trapping, and stoichiometric model reaction studies. Specifically, the amination of 2-methyl-2-hexene by (dipic)(HMPA)Mo(eta(2)-PhNO) (1a, dipic = 2,6-pyridinedicarboxylate; HMPA = hexamethylphosphoric triamide) is found to be first order in la and zeroth order in olefin and HMPA. Evidence for dissociation of nitrosobenzene from la is provided by trapping of the latter as a hetero-Diels-Alder adduct with 2,3-dimethylbutadiene and by exchange experiments of la with free aryl nitroso compounds. A competing pathway involving extrusion of aryl nitrene from la is also implicated by the production of carbazole from the thermolysis of (dipic)(HMPA)Mo(eta(2)-2-C6H5-C6H4NO) (5) The findings that (1) the ene reaction of nitrosobenzene with 2-methyl-2-hexene occurs readily (less than or equal to 70 degrees C) and regioselectively to produce allyl hydroxylamine 7 and (2) that Mo(IV) complexes (dedtc)(2)MoO (3b, dedtc = N,N-diethyldithiocarbamate) and (dipic)(HMPA)MoO (3a) readily deoxygenate arylhydroxylamines (including 7) support the involvement of these steps in the amination process. Control experiments and model reaction studies have identified some of the pathways for the formation of the byproducts, aniline and azoxybenzene. Together the above results indicate that the primary pathway for Mo-promoted olefin allylic amination involves: (1) reaction of LL'Mo(VI)O-2 with RNHOH to form a molybdooxaziridine 1 (and water); (2) dissociation of 1 to form RNO and LL'Mo(IV)O (3);(3) ene-reaction of RNO with the olefin to produce an N-allyl hydroxylamine; and (4) reduction of the allyl hydroxylamine by 3, yielding the allyl amine and regenerating LL'Mo(VI)O-2 (2).

  DOI：

  10.1021/jo00097a044

文献信息

• Mechanistic Aspects of Molybdenum-Promoted Allylic Amination
  作者：Radhey S. Srivastava、Kenneth M. Nicholas

  DOI：10.1021/jo00097a044

  日期：1994.9

  The mechanism of molybdenum-mediated allylic amination by phenylhydroxylamine has been probed through a variety of kinetics, trapping, and stoichiometric model reaction studies. Specifically, the amination of 2-methyl-2-hexene by (dipic)(HMPA)Mo(eta(2)-PhNO) (1a, dipic = 2,6-pyridinedicarboxylate; HMPA = hexamethylphosphoric triamide) is found to be first order in la and zeroth order in olefin and HMPA. Evidence for dissociation of nitrosobenzene from la is provided by trapping of the latter as a hetero-Diels-Alder adduct with 2,3-dimethylbutadiene and by exchange experiments of la with free aryl nitroso compounds. A competing pathway involving extrusion of aryl nitrene from la is also implicated by the production of carbazole from the thermolysis of (dipic)(HMPA)Mo(eta(2)-2-C6H5-C6H4NO) (5) The findings that (1) the ene reaction of nitrosobenzene with 2-methyl-2-hexene occurs readily (less than or equal to 70 degrees C) and regioselectively to produce allyl hydroxylamine 7 and (2) that Mo(IV) complexes (dedtc)(2)MoO (3b, dedtc = N,N-diethyldithiocarbamate) and (dipic)(HMPA)MoO (3a) readily deoxygenate arylhydroxylamines (including 7) support the involvement of these steps in the amination process. Control experiments and model reaction studies have identified some of the pathways for the formation of the byproducts, aniline and azoxybenzene. Together the above results indicate that the primary pathway for Mo-promoted olefin allylic amination involves: (1) reaction of LL'Mo(VI)O-2 with RNHOH to form a molybdooxaziridine 1 (and water); (2) dissociation of 1 to form RNO and LL'Mo(IV)O (3);(3) ene-reaction of RNO with the olefin to produce an N-allyl hydroxylamine; and (4) reduction of the allyl hydroxylamine by 3, yielding the allyl amine and regenerating LL'Mo(VI)O-2 (2).