N-(3,5-dimethylphenyl)-1,1-diphenylmethanimine | 384344-10-9

• 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-(3,5-dimethylphenyl)-1,1-diphenylmethanimine
• 英文别名: N-(diphenyl methylene)-3,5-dimethylaniline；N-(3,5-Dimethylphenyl)benzophenone imine
• CAS: 384344-10-9
• 化学式: C₂₁H₁₉N
• 分子量: 285.389
• InChiKey: OVOKGMSFXVWRHU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(3,5-dimethylphenyl)-1,1-diphenylmethanimine 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  EPR and ENDOR study of chiral nitroxides

  摘要：

  在不同温度下对外消旋和非手性烷基芳基硝基化合物进行了研究。β-质子耦合常数和芳香族正质子的不等价性都表明，氨基羟基取代基的旋转受到了限制。对这些结果的解释是，存在两种不同的旋转体，这可能会导致 β-质子有两个分裂常数。所研究的硝基氧化物都能在分子间和分子内形成氢键。然而，由手性基和手性辅助剂组成的复合物并没有显示出明确表示非对映异构体的超精细结构。因此，如果不改变超共轭角，手性分子之间的氢键不足以实现手性识别。简单的立体相互作用就能使β-质子耦合常数加倍，而与非对映异构体复合物的形成无关。

  DOI：

  10.1002/mrc.1260270912
• 作为产物：
  描述：

  二苯甲酮亚胺 、 3,5-二甲基溴苯 在 potassium tert-butylate 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 、 1,3-双(2,6-二异丙基苯基)氯化咪唑鎓 作用下， 以 1,4-二氧六环 为溶剂， 反应 10.0h， 以99%的产率得到N-(3,5-dimethylphenyl)-1,1-diphenylmethanimine
  参考文献：
  名称：

  钯/咪唑鎓盐系统介导的芳基卤化物与含氮试剂的胺化反应。

  摘要：

  亲核N-杂环卡宾已被方便地用作胺改性反应的催化剂改性剂，该反应涉及芳基氯化物，芳基溴化物和芳基碘化物与各种含氮底物。使用各种底物测试了在碱，KO（t）Bu或NaOH存在下使用Pd（0）或Pd（II）源和咪唑鎓盐进行偶联过程的范围。Pd（2）（dba）（3）/IPr.HCl（1，IPr = 1,3-双（2,6-二异丙基苯基）咪唑-2-亚烷基）体系相对于电子中性和富电子的芳基氯化物。该配体对于二苯甲酮亚胺的合成也是有效的，其可以通过酸水解容易地转化为相应的伯胺。使用较多的SIPr.HCl（5，SIPr ＝ 1，3-双（2，6-二异丙基苯基）-4，5-二氢咪唑-2-亚烷基。Pd（OAc）（2）/SIPr.HCl/NaOH系统可有效用于各种吲哚与芳基溴的N-芳基化反应。所开发的通用方案已成功应用于重要的新抗生素合成中的关键中间体的合成。从机理上讲，钯与配体的比例研究强有力地支持了带有一个亲核卡宾配体的活性物质。

  DOI：

  10.1021/jo010613+

文献信息

• Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds
  申请人：——

  公开号：US20030065187A1

  公开（公告）日：2003-04-03

  The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In additional embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between a nitrogen atom of an acyl hydrazine and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of a nitrogen-containing heteroaromatic, e.g., indole, pyrazole, and indazole, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-oxygen bond between the oxygen atom of an alcohol and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The present invention also relates to copper-catalyzed methods of forming a carbon-carbon bond between a reactant comprising a nucleophilic carbon atom, e.g., an enolate or malonate anion, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. Importantly, all the methods of the present invention are relatively inexpensive to practice due to the low cost of the copper comprised by the catalysts.

  本发明涉及铜催化的碳-杂原子和碳-碳键形成方法。在某些实施例中，本发明涉及铜催化的方法，用于在酰胺或胺基团的氮原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氮键。在其他实施例中，本发明涉及铜催化的方法，用于在酰基肼的氮原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氮键。在另一些实施例中，本发明涉及铜催化的方法，用于在含氮杂环芳烃（例如吲哚、吡唑和吲哌）的氮原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氮键。在某些实施例中，本发明涉及铜催化的方法，用于在醇的氧原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氧键。本发明还涉及铜催化的方法，用于在包含亲核碳原子的反应物（例如烯醇酸盐或丙二酸盐负离子）与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-碳键。重要的是，由于催化剂中铜的低成本，本发明的所有方法都相对廉价。
• Copper-catalyzed formation of carbon heteroatom and carbon-carbon bonds
  申请人：Buchwald L. Stephen

  公开号：US20050215794A1

  公开（公告）日：2005-09-29

  The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In additional embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between a nitrogen atom of an acyl hydrazine and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of a nitrogen-containing heteroaromatic, e.g., indole, pyrazole, and indazole, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-oxygen bond between the oxygen atom of an alcohol and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The present invention also relates to copper-catalyzed methods of forming a carbon-carbon bond between a reactant comprising a nucleophilic carbon atom, e.g., an enolate or malonate anion, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. Importantly, all the methods of the present invention are relatively inexpensive to practice due to the low cost of the copper comprised by the catalysts.

  本发明涉及铜催化的碳-杂原子和碳-碳键形成方法。在某些实施例中，本发明涉及铜催化的方法，用于在苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳和酰胺或胺基团的氮原子之间形成碳-氮键。在其他实施例中，本发明涉及铜催化的方法，用于在苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳和酰肼的氮原子之间形成碳-氮键。在其他实施例中，本发明涉及铜催化的方法，用于在苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳和含氮杂环芳香族化合物（例如吲哚、吡唑和吲唑）的氮原子之间形成碳-氮键。在某些实施例中，本发明涉及铜催化的方法，用于在苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳和醇的氧原子之间形成碳-氧键。本发明还涉及铜催化的方法，用于在包含亲核碳原子（例如烯醇酸根离子或马隆酸根离子）的反应物和苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳之间形成碳-碳键。重要的是，由于催化剂中铜的低成本，本发明的所有方法都相对廉价易行。
• Copper-catalyzed formation of carbon-heteroatom and carbon—carbon bonds
  申请人：Buchwald Stephen L.

  公开号：US09067955B2

  公开（公告）日：2015-06-30

  The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods, such as the reaction of Z-X with C(L)(R)(R′)2 in the present of a catalyst and a base, thereby forming C(Z)(R)(R′)2; wherein X represents I, Cl, alkylsulfonate, or arylsulfonate; Z represents optionally substituted aryl, heteroaryl or alkenyl; L represents H or a negative charge; catalyst comprises a copper atom or ion, and a ligand, wherein the ligand is an optionally substituted aryl alcohol, alkyl amine, 1,2-diamine, 1,2-aminoalcohol, 1,2-diol, imidazolium carbene, pyridine, or 1,10-phenanthroline; the ligand is a chelating ligand; and the base represents a Bronsted base; R represents H, optionally substituted alkyl, cycloalkyl, aralkyl, aryl, or heteroaryl; R′ represents independently for each occurrence H, alkyl, cycloalkyl, aralkyl, aryl, or heteroaryl, formyl, acyl, —CO2R″, —C(O)N(R)2, sulfonyl, —P(O)(OR″)2, —CN, or —NO2; R″ represents independently for each occurrence optionally substituted alkyl, cycloalkyl, aralkyl, aryl, or heteroaryl; and C(R′)2(R) taken together may represent nitrile.

  本发明涉及铜催化的碳-杂原子和碳-碳键形成方法，例如在催化剂和碱的存在下，Z-X与C（L）（R）（R'）2反应，从而形成C（Z）（R）（R'）2；其中X代表I，Cl，烷基磺酸盐或芳基磺酸盐；Z代表可选取代的芳基，杂原芳基或烯丙基；L代表H或负电荷；催化剂包括铜原子或离子和配体，其中配体是可选取代的芳基醇，烷基胺，1,2-二胺，1,2-氨基醇，1,2-二醇，咪唑卡宾，吡啶或1,10-菲啰啉；配体是螯合配体；碱代表布朗斯特德碱；R代表H，可选取代的烷基，环烷基，芳基烷基，芳基或杂原芳基；R'代表独立地为每个出现的H，烷基，环烷基，芳基烷基，芳基或杂原芳基，甲酰基，酰基，-CO2R″，-C（O）N（R）2，磺酰基，-P（O）（OR″）2，-CN或-NO2；R″代表独立地为每个出现的可选取代的烷基，环烷基，芳基烷基，芳基或杂原芳基；而C（R'）2（R）在一起可以代表腈。
• Palladium-Catalyzed Diarylation of Isocyanides with Tetraarylleads for the Selective Synthesis of Imines and α-Diimines
  作者：Cong Chi Tran、Shin-ichi Kawaguchi、Yohsuke Kobiki、Hitomi Matsubara、Dat Phuc Tran、Shintaro Kodama、Akihiro Nomoto、Akiya Ogawa

  DOI：10.1021/acs.joc.9b01639

  日期：2019.9.20

  Using tetraaryllead compounds (PbAr4) as arylating reagents, isocyanides undergo selective diarylation in the presence of palladium catalysts such as Pd(OAc)(2) or Pd(PPh3)(4) to afford imines and/or alpha-diimines based on the isocyanide employed. With aliphatic isocyanides, imines are obtained preferentially, whereas alpha-diimines are formed in the case of electron-rich aromatic isocyanides. The differences in imine/alpha-diimine selectivity can be attributed to the stability of imidoylpalladium intermediates formed in this catalytic reaction. Compared with other arylating reagents, tetraaryllead compounds are excellent candidates for use in the selective transformations to imines and/or alpha-diimines, especially in terms of inhibiting the oligomerization of isocyanides, which results in a lower product selectivity in many transition-metal-catalyzed reactions of isocyanides.
• COPPER-CATALYZED FORMATION OF CARBON-HETEROATOM AND CARBON-CARBON BONDS
  申请人：MASSACHUSETTS INSTITUTE OF TECHNOLOGY

  公开号：EP1390340A1

  公开（公告）日：2004-02-25