N-(2-methoxyphenyl)-1-(4-nitrophenyl)methanimine | 156300-65-1

• 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-(2-methoxyphenyl)-1-(4-nitrophenyl)methanimine
• 英文别名: (2-methoxyphenyl)[(E)-(4-nitrophenyl)methylidene]amine；N-(2-methoxyphenyl)-4-nitrobenzylideneamine；6-methoxy-N-(4-nitrobenzylidene)aniline
• CAS: 156300-65-1
• 化学式: C₁₄H₁₂N₂O₃
• 分子量: 256.261
• InChiKey: VKFXDMFWDUDNCV-XNTDXEJSSA-N

物化性质

• 沸点：
  453.0±30.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.35
• 重原子数：
  19.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  64.73
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  mercury(II) diacetate 、 N-(2-methoxyphenyl)-1-(4-nitrophenyl)methanimine 以 甲醇 为溶剂， 以85%的产率得到2,4-bis(acetatomercurio)-6-methoxy-N-(4-nitrobenzylidene)aniline
  参考文献：
  名称：

  Mercuration of Schiff bases of substituted benzylideneanilines

  摘要：

  As part of an effort to investigate substituent effects on the intramolecular coordination between N and Hg, the mercuration of 36 substituted benzylideneanilines was studied. The structure characterization of the products by IR, H-1 NMR, C-13 NMR, and MS indicates that for all of the reactions examined, the mercury is directed to the ortho position of the N-phenyl ring or the para position of the N-phenyl ring when these sites are not occupied by a substituent. The position of the HgCl group in the mercurated product of N-(4-nitrobenzylidene)-beta-naphthylamine has been confirmed by single-crystal X-ray determination, which also provided circumstantial evidence for the existence of the N--> Hg intramolecular coordination with a four-membered ring. The possible mechanism of the reaction was proposed, in which the mercuration at the ortho position of the N-phenyl ring was facilitated by the imino moiety upon formation of a coordination complex with Hg(OAc)2 in the first step, followed by a subsequent electrophilic substitution at the ortho position of the N-phenyl ring. This reaction is different from the metalation of benzylideneanilines by transition metals, in which the metal atom is usually directed to the ortho position of the C-phenyl ring, and provides a new example of the so-called 'cyclometalation" reaction.

  DOI：

  10.1021/om00059a058
• 作为产物：
  描述：

  邻甲氧基苯胺 、 对硝基苯甲醛 以 乙醇 为溶剂， 反应 0.5h， 生成 N-(2-methoxyphenyl)-1-(4-nitrophenyl)methanimine
  参考文献：
  名称：

  The effect of molecular planarity on crystal non-centrosymmetry in benzylidene–aniline derivatives

  摘要：

  In the title compound, N-(2-methoxyphenyl)-4-nitrobenzylideneamine, C(14)H(12)N(2)O(3), the two phenyl rings make a dihedral angle of 48.0 (2) degrees and the nitro group is at an angle of 6.5 (1) degrees with respect to its attached phenyl ring. In the crystal structure, molecules are related as centrosymmetric pairs through pi-pi interactions and are further connected through strong C[bond]H...O hydrogen bonds [C...O 3.4259 (17) A and C[bond]H...O 167 degrees ], forming molecular stacks along [100]. These stacks associate further through longer C[bond]H...O interactions, forming two-dimensional networks. In the c direction, there are only weak van der Waals interactions. The relationship between the molecular planarity and its centrosymmetry is also briefly described.

  DOI：

  10.1107/s0108270102006479

文献信息

• Ag-Catalyzed Asymmetric Mannich Reactions of Enol Ethers with Aryl, Alkyl, Alkenyl, and Alkynyl Imines
  作者：Nathan S. Josephsohn、Marc L. Snapper、Amir H. Hoveyda

  DOI：10.1021/ja049388e

  日期：2004.3.1

  An efficient catalytic and enantioselective method (up to >98% ee) for Mannich reactions between trimethylsilyl enol ethers derived from acetone and acetophenone and aryl, alkenyl, alkynyl, and alkyl imines is disclosed. A large variety of beta-amino ketones can be synthesized in the presence of 1-5 mol % AgOAc and an inexpensive and readily available amino acid-derived phosphine. All Ag-catalyzed

  公开了一种有效的催化和对映选择性方法（高达 >98% ee），用于衍生自丙酮和苯乙酮的三甲基甲硅烷基烯醇醚与芳基、烯基、炔基和烷基亚胺之间的曼尼希反应。在 1-5 mol% AgOAc 和廉价且容易获得的氨基酸衍生膦存在下，可以合成多种 β-氨基酮。所有 Ag 催化的不对称曼尼希反应都可以在未蒸馏的 THF 和空气中进行。产品胺的邻茴香基活化基团可以通过单容器操作以 >70% 的分离产率去除。催化不对称方法的合成效用通过光学纯生物碱 (-)-sedamine 的四锅合成来说明。
• Unexpected Domino Synthesis of Complex Angular Naphthoimidazoles
  作者：Gema Guedes、Matías López-Rodríguez、Angel G. Ravelo、Ana Estévez-Braun

  DOI：10.1002/ejoc.201200625

  日期：2012.10

  Several disubstituted angular naphthoimidazoles have been synthesized by a new domino reaction from (1,4-dimethoxynaphthalen-2-yl)amine (1) and imines (obtained from 1 and aromatic aldehydes) in the presence of Sc(OTf)3. A plausible pathway for the reaction involves attack of the nucleophilic amine on the imine and further reaction of the resulting intermediate by intramolecular cyclization with loss

  在 Sc(OTf)3 存在下，通过 (1,4-二甲氧基萘-2-基) 胺 (1) 和亚胺（从 1 和芳香醛获得）的新多米诺反应合成了几种双取代的有角萘并咪唑。该反应的一个可能的途径包括亲核胺对亚胺的攻击和所得中间体的进一步反应，通过分子内环化失去甲氧基，随后氧化产生最终的萘并咪唑。这些萘并咪唑也以较低的收率从芳香醛、Sc(OTf)3 和 2 当量中获得。1 通过 ABB' 多米诺骨牌过程。后缩合转换允许直接访问几种衍生物。
• Amine-catalyzed direct asymmetric Mannich-type reactions
  作者：Wolfgang Notz、Kandasamy Sakthivel、Tommy Bui、Guofu Zhong、Carlos F Barbas

  DOI：10.1016/s0040-4039(00)01908-0

  日期：2001.1

  Three chiral cyclic secondary amines are shown to be catalysts for the direct asymmetric Mannich-type reaction of acetone with a variety of preformed aldimines derived from o-anisidine. A simple one-pot three-component reaction procedure consisting of aldehyde, acetone, p-anisidine and an amine catalyst provides the corresponding β-amino ketones with 50–89% ee under very mild conditions.

  三种手性环状仲胺被证明是丙酮与各种衍生自邻氨基苯甲醚的预制醛亚胺直接不对称曼尼希型反应的催化剂。由乙醛，丙酮，对氨基苯甲酸和胺催化剂组成的简单的一锅式三组分反应程序在非常温和的条件下可提供具有50-89％ee的相应β-氨基酮。
• A Highly Efficient and Practical Method for Catalytic Asymmetric Vinylogous Mannich (AVM) Reactions
  作者：Emma L. Carswell、Marc L. Snapper、Amir H. Hoveyda

  DOI：10.1002/anie.200603496

  日期：2006.11.6
• Efficient and Practical Ag-Catalyzed Cycloadditions between Arylimines and the Danishefsky Diene
  作者：Nathan S. Josephsohn、Marc L. Snapper、Amir H. Hoveyda

  DOI：10.1021/ja030033p

  日期：2003.4.1

  An efficient Ag-catalyzed method for asymmetric addition of the Danishefsky diene to various aryl imines to afford cycloadducts in > or =89% ee and > or =85% isolated yield is reported. Reactions are effected with 0.1-1 mol % catalyst (4 degrees C), and the chiral ligand is readily prepared from commercially available materials, including the inexpensive i-Leu. These catalytic asymmetric cycloadditions can be carried out without the use of solvent or with undistilled THF in air. A first generation supported chiral catalyst that effectively promotes the cycloaddition reaction and can be recycled (five cycles) is described.