[1-(3-Nitro-phenyl)-meth-(E)-ylidene]-propyl-amine | 164402-30-6

• 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: [1-(3-Nitro-phenyl)-meth-(E)-ylidene]-propyl-amine
• 英文别名: 1-(3-nitrophenyl)-N-propylmethanimine
• CAS: 164402-30-6
• 化学式: C₁₀H₁₂N₂O₂
• 分子量: 192.217
• InChiKey: MHKAGCKLDQKVGH-UHFFFAOYSA-N

物化性质

• 沸点：
  304.3±25.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  58.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [1-(3-Nitro-phenyl)-meth-(E)-ylidene]-propyl-amine 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以1.87 g的产率得到N-propyl-3-nitrobenzylamine
  参考文献：
  名称：

  Preparation of Benzolactams by Pd(OAc)₂-Catalyzed Direct Aromatic Carbonylation

  摘要：

  We developed a new method for Pd(II)-catalyzed direct aromatic carbonylation in a phosphine-free catalytic system using Pd(OAc)2 and Cu(OAc)2 in an atmosphere of CO gas containing air. The carbonylation proceeded with ortho-palladation, inducing a remarkable site selectivity to afford a variety of five- or six-membered benzolactams from secondary omega-arylalkylamines, such as N-alkylbenzylamines or N-alkylphenethylamines.

  DOI：

  10.1021/ja045342+
• 作为产物：
  描述：

  正丙胺 、 间硝基苯甲醛 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 反应 0.5h， 生成 [1-(3-Nitro-phenyl)-meth-(E)-ylidene]-propyl-amine
  参考文献：
  名称：

  从亚胺、有机锌试剂和酰氯或氯甲酸酯获得叔二芳基甲基酰胺或氨基甲酸酯的实用途径。

  摘要：

  描述了从亚胺、有机锌试剂和酰氯或氯甲酸酯获得叔二芳基甲基酰胺或氨基甲酸酯的实用途径。该路线涉及形成亚胺，无需分离即可使用，然后通过含羰基的亲电子试剂对其进行活化，并通过有机锌试剂捕获酰基胺。大多数步骤同时进行，以使程序尽可能实用和直接。因此，整个实验协议需要不到两个小时。

  DOI：

  10.3762/bjoc.7.112

文献信息

• Ortho-Nitro Effect on the Diastereoselective Control in Sulfa-Staudinger and Staudinger Cycloadditions
  作者：Zhanhui Yang、Hassane Abdellaoui、Wei He、Jiaxi Xu

  DOI：10.3390/molecules22050784

  日期：——

  The ortho-nitro effect was discovered in sulfa-Staudinger cycloadditions of ethoxycarbonylsulfene with linear imines. When an ortho-nitro group is present at the C-aryl substituents of linear imines, the sulfa-Staudinger cycloadditions deliver cis-β-sultams in considerable amounts, together with the predominant trans-β-sultams. In other cases, the above sulfa-Staudinger cycloadditions give rise to trans-β-sultams

  在乙氧基羰基亚砜与线性亚胺的磺胺-施陶丁格环加成反应中发现了邻硝基作用。当直链亚胺的C-芳基取代基上存在邻硝基时，磺胺-施陶丁格环加成物将以大量的顺式-β-杜鹃花与主要的反式-β-杜鹃花一起递送。在其他情况下，上述磺胺-施陶丁格环加成仅产生反式-β-杜鹃花。进一步的机械合理化揭示了邻硝基效应归因于其强大的吸电子诱导效应。同样，邻硝基效应也存在于乙氧基羰基乙烯酮与亚胺的斯托丁格环加成中。目前的研究为磺胺-施陶丁格和施陶丁格环加成中的非对映选择性控制提供了进一步的见解。
• Catalytic aza-Nazarov cyclization reactions to access α-methylene-γ-lactam heterocycles
  作者：Bilge Banu Yagci、Selin Ezgi Donmez、Onur Şahin、Yunus Emre Türkmen

  DOI：10.3762/bjoc.19.6

  日期：——

  full diastereocontrol (dr = >99:1). The use of acyclic imines in a similar catalytic aza-Nazarov reaction with 20 mol % of AgOTf results in the formation of α-methylene-γ-lactam heterocycles 19 in up to 76% yield and with good to high diastereoselectivities (4.3:1 to 16:1). We have demonstrated the scalability of the reaction with a gram-scale example. The relative stereochemistry of the α-methylene-γ-lactam

  我们开发了一种催化氮杂-纳扎罗夫反应，通过多种环状和无环亚胺与α,β-不饱和酰氯的反应原位生成N-酰亚胺盐，得到取代的α-亚甲基-γ-内酰胺杂环。该反应在催化量（20 mol%）AgOTf（作为阴离子交换剂）或氢键供体（例如方酰胺和硫脲）作为阴离子结合有机催化剂的存在下有效进行。 3,4-二氢异喹啉与 α,β-不饱和酰氯的氮杂-纳扎罗夫环化得到三环内酰胺产物7 ，产率高达 79%，且完全非对映控制 (dr = >99:1)。在类似的催化氮杂-纳扎罗夫反应中使用无环亚胺与 20 mol% AgOTf 会形成 α-亚甲基-γ-内酰胺杂环19 ，产率高达 76%，并且具有良好至高的非对映选择性（4.3:1 至16:1）。我们通过克级示例证明了反应的可扩展性。 α-亚甲基-γ-内酰胺产物19的相对立体化学已通过内酰胺19l的单晶X射线分析确定。为了阐明反应机理的细节，我们进行了精心设计的机理研究，其中包括
• Benzylamines: synthesis and evaluation of antimycobacterial properties
  作者：Wolfgang R. Meindl、Erwin Von Angerer、Helmut Schoenenberger、Gotthard Ruckdeschel

  DOI：10.1021/jm00375a005

  日期：1984.9

  The synthesis of benzylamines with various N-alkyl chains and substituents in the aromatic system as well as their evaluation on Mycobacterium tuberculosis H 37 Ra are described. The most active compounds in this test, N-methyl-3-chlorobenzylamine (19, MIC 10.2 micrograms/mL), N-methyl-3,5-dichlorobenzylamine (93, MIC 10.2 micrograms/mL), and N-butyl-3,5-difluorobenzylamine (103, MIC 6.4 micrograms/mL), also exhibited a marked inhibitory effect on Mycobacterium marinum and Mycobacterium lufu used for the determination of antileprotic properties. The combinations of 93 with aminosalicylic acid, streptomycin, or dapsone exert marked supra-additive effects on M. tuberculosis H 37 Ra.
• Separation of Ring Polar and Resonance Effects on the Rate Constants for Uncatalyzed N-Arylidenepropylamine Formation in Methanol
  作者：Jean Toullec、Didier Milin

  DOI：10.1021/jo00089a033

  日期：1994.5

  Rate constants are reported for the reaction of a series of 19 ring-substituted benzaldehydes with propylamine in methanol and in O-d-methanol at different temperatures and of three of them with 2-methoxyethylamine and 2,2-dimethoxyethylamine. The large direct solvent kinetic isotope effects (KSIE) (2.1-2.9), as well as the Delta H* (4.7-7.6 kcal mol(-1)) values vary smoothly with substituent. Delta S* (ca. -45 cal mol(-1) K-1) is almost independent of substituent. These data indicate that there in no change in the rate-limiting step, and since the large KSIE and \Delta S*\ can be related to significant solvation of the leading OH- group at the transition state, they agree with a mechanism involving cu-amino alcohol formation in a fast preequilibrium followed by rate-limiting OH- detachment yielding iminium ions. When corrected for parallel hemiacetal formation, the second-order rate constants are accounted for by the Young-Jencks equation with p(n) = 0.08 and p(r) = 0.57, this equation allowing a separation of the direct resonance effects from the polar effects of the substituted ring. The very low p(n) value indicates that the polar effects for the rate-limiting OH- detachment are almost compensated by those on the constant of the alpha-amino alcohol-formation preequilibrium. In contrast, the relatively large p(r) coefficient, which means that the overall rate constants depend almost exclusively on resonance, is due to predominance of the direct resonance effects on the preequilibrium. The KSIE and Delta S* data, as well as the beta(nucl) parameters (close to unity) observed when the reacting amine was changed (slopes of the straight lines obtained by plotting the logarithm of the rate constants vs the pK(a) of the ammonium ions) favor a late transition state. In contrast, the low p(r) value for the rate-limiting step (ca. -0.5) shows that the transition state is not iminium ion-like.