N-(2-methylhex-1-en-3-yl)aniline | 142836-00-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-(2-methylhex-1-en-3-yl)aniline
• CAS: 142836-00-8
• 化学式: C₁₃H₁₉N
• 分子量: 189.301
• InChiKey: QLYHYIHEIBMWOD-UHFFFAOYSA-N

物化性质

• 沸点：
  286.1±9.0 °C(Predicted)
• 密度：
  0.931±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  14
• 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：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2-甲基-2-己烯 、 苯基羟胺 在 iron(III) chloride hexahydrate 、 iron(II) chloride 作用下， 以 1,4-二氧六环 为溶剂， 反应 8.0h， 以50%的产率得到N-(2-methylhex-1-en-3-yl)aniline
  参考文献：
  名称：

  铁盐催化的区域选择性烯丙基胺化

  摘要：

  烯烃在Fe（II）和Fe（III）盐存在下与苯基羟胺反应，以中等至良好的收率生产N-苯基-N-烯丙基胺。不对称的底物以高区域选择性反应，产生双键易位产物。

  DOI：

  10.1016/s0040-4039(00)78485-1

文献信息

• On the Mechanism of Allylic Amination Catalyzed by Iron Salts
  作者：Radhey S. Srivastava、Kenneth M. Nicholas

  DOI：10.1021/ja964006t

  日期：1997.4.1

  high regioselectivity resulting from double-bond transposition. The iron-catalyzed reaction of phenylhydroxylamine with representative alkenes in the presence of 2,3-dimethylbutadiene, an effective PhNO trap, produces allyl amines exclusively, excluding the intermediacy of free PhNO in the amination reaction. The reaction of FeCl2,3 with PhNO or PhNHOH produces a novel azo dioxide iron complex, Fe

  铁盐催化芳基羟胺对烯烃的烯丙基胺化反应，产率中等至良好，双键转座具有高区域选择性。在 2,3-二甲基丁二烯（一种有效的 PhNO 捕集剂）存在下，苯基羟胺与代表性烯烃的铁催化反应仅产生烯丙胺，不包括游离 PhNO 在胺化反应中的中介作用。FeCl2,3 与 PhNO 或 PhNHOH 反应产生一种新型的偶氮二氧化铁络合物 Fe[Ph(O)NN(O)Ph]3}[FeCl4]2 (1a)，其结构已通过 X 射线确定衍射。1a 的结构基本上具有四面体 Fe(III)Cl4- 阴离子和一种新型六配位二价阳离子，其中铁 (II) 通过三个偶氮苯 N,N-二氧化物配体的氧结合。1a 是催化反应中活性胺化剂的证据包括（1）它与催化反应的分离；(2) 与烯烃反应容易，以高产率和区域选择性生产烯丙胺；（……
• Mechanistic Studies of Copper(I)-Catalyzed Allylic Amination
  作者：Radhey S. Srivastava、Nathan R. Tarver、Kenneth M. Nicholas

  DOI：10.1021/ja0751072

  日期：2007.12.1

  novel Cu(I) complexes, [Cu(PhNO)3]PF6 (1) and [Cu(Et2NPhNO)3]PF6 (2); in 2 the copper atom is N-coordinated to the nitrosoarenes in a distorted trigonal planar geometry. Complex 1 is strongly implicated as a reactive intermediate in the Cu(I)-catalyzed allylic amination of olefins based on (i) its isolation from the catalytic reaction, (ii) its stoichiometric regioselective allylic amination of alpha-methyl

  亚硝基苯和 N,N'-二乙基-4-亚硝基苯胺与 [Cu(CH3CN)4]PF6 的反应提供了新的 Cu(I) 配合物，[Cu(PhNO)3]PF6 (1) 和 [Cu(Et2NPhNO)3 ]PF6 (2); 在 2 中，铜原子在扭曲的三角平面几何形状中与亚硝基芳烃 N 配位。基于 (i) 从催化反应中分离，(ii) α-甲基苯乙烯 (AMS) 的化学计量区域选择性烯丙基胺化，配合物 1 被强烈暗示为 Cu(I) 催化的烯烃烯丙基胺化中的反应中间体， (iii) 游离 PhNO 不参与 AMS 的胺化，以及 (iv) 其作为从苯羟胺胺化烯烃的催化剂的功能。AMS 和 1（80 摄氏度，二恶烷）之间的反应在烯烃和 1 中都是一级反应。1 与对位取代的 AMS 衍生物反应的相对速率研究给出了 -0.035 的哈米特 rho 值。根据光谱表征和热解，从 1 与苯乙烯和 α-甲基苯乙烯的反应中分离出的烯烃加合物被配制成
• Molybdenum-catalysed allylic amination
  作者：Anurag Srivastava、You-An Ma、Ratnadevi Pankayatselvan、Warren Dinges、Kenneth M. Nicholas

  DOI：10.1039/c39920000853

  日期：——

  Dioxomolybdenum(VI) complexes including MoO2(dipic)(HMPA)2a and MoO2(dedtc)22b(dipic = 2,6-pyridinedicarboxylate; HMPA = hexamethylphosphoramide; dedtc =N,N-diethyl dithiocarbamate) catalyse the allylic amination of alkenes by phenyl hydroxylamine; the reactions are characterized by a high degree of regioselectivity resulting from double bond migration.

  包括 MoO2(dipic)(HMPA)2a 和 MoO2(dedtc)22b（dipic = 2,6-吡啶二甲酸酯；HMPA = 六甲基磷酰胺；dedtc = N,N-二乙基二硫代氨基甲酸酯）在内的二氧代钼（VI）配合物能催化苯基羟胺对烯的烯丙基胺化反应；反应的特点是双键迁移产生的高度区域选择性。
• 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).
• Regioselective allylic amination catalyzed by iron salts
  作者：Radhey S. Srivastava、Kenneth M. Nicholas

  DOI：10.1016/s0040-4039(00)78485-1

  日期：1994.11

  Alkenes react with phenylhydroxylamine in the presence of Fe(II) and Fe(III) salts to produce N-phenyl-N-allyl amines in moderate to good yields. Unsymmetrical substrates react with high regioselectivity giving the products of double bond transposition.

  烯烃在Fe（II）和Fe（III）盐存在下与苯基羟胺反应，以中等至良好的收率生产N-苯基-N-烯丙基胺。不对称的底物以高区域选择性反应，产生双键易位产物。