N-(2-bromobenzylidene)-1-phenylmethanamine | 108791-78-2

• 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-bromobenzylidene)-1-phenylmethanamine
• 英文别名: N-(2-bromobenzylidene)benzylamine；N-benzyl-1-(2-bromophenyl)methanimine
• CAS: 108791-78-2
• 化学式: C₁₄H₁₂BrN
• 分子量: 274.16
• InChiKey: HGWRPOZQQTVIGV-UHFFFAOYSA-N

物化性质

• 沸点：
  362.7±35.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 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-(2-bromobenzylidene)-1-phenylmethanamine 以 丙酮 、 甲苯 为溶剂， 反应 20.5h， 生成 [PtBr{2-MeC6H3CH=NCH2(C6H5)}PPh3]
  参考文献：
  名称：

  Regioselective C–H Activation Preceded by C_sp²–C_sp³ Reductive Elimination from Cyclometalated Platinum(IV) Complexes

  摘要：

  Reductive elimination reactions of the cyclometalated platinum-(IV) compounds [PtMe2Cl{C6H4CH=NCH2(4-ClC6H4)}L] and [PtMe2Br{C6H4CH=NCH2(C6H5)}L] (L = SMe2, PPh3) to form C-sp3-C-sp2 bonds, followed by either exclusive C H bond activation (L = SMe2) or competition between C-sp2-H and C-sp3-H bond activation (L = PPh3), are reported. Isomerization to give endo products instead of the expected exo complex was observed for the ligand C6H4CH=NCH2(2-BrC6H5), and formation of an endo six-membered platinacycle occurs for the ligand 2,4,6-Me3C6H2CH=NCH2(2-BrC6H4).

  DOI：

  10.1021/om400398g
• 作为产物：
  描述：

  2-溴苄醇 在 2-碘酰基苯甲酸 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 1.0h， 生成 N-(2-bromobenzylidene)-1-phenylmethanamine
  参考文献：
  名称：

  Ugi Four-Component Reaction of Alcohols: Stoichiometric and Catalytic Oxidation/MCR Sequences

  摘要：

  A new, simple, and efficient procedure for the one-pot Ugi four-component reaction of alcohols instead of aldehydes is described. Using a stoichiometric amount of IBX or only 1-2% of sodium 2-iodobenzenesulfonate in the presence of Oxone, a wide range of primary alcohols were oxidized to the aldehyde that were directly engaged in the Ugi four-component reaction to afford alpha-acetamidoamides in good to excellent yields.

  DOI：

  10.1021/ol401181a

文献信息

• Highly Enantioselective Titanium-Catalyzed Cyanation of Imines at Room Temperature
  作者：Abdul Majeed Seayad、Balamurugan Ramalingam、Kazuhiko Yoshinaga、Takushi Nagata、Christina L. L. Chai

  DOI：10.1021/ol902540h

  日期：2010.1.15

  A highly active and enantioselective titanium-catalyzed cyanation of imines at room temperature is described. The catalyst used is a partially hydrolyzed titanium alkoxide (PHTA) precatalyst together with a readily available N-salicyl-β-aminoalcohol ligand. Up to 98% ee was obtained with quantitative yields in 15 min of reaction time using 5 mol % of the catalyst. Various N-protecting groups such as

  描述了在室温下高活性和对映选择性的钛催化的亚胺氰化。所用的催化剂是部分水解的烷氧基钛（PHTA）预催化剂以及易于获得的N-水杨基-β-氨基醇配体。使用5 mol％的催化剂，在15分钟的反应时间内以定量收率获得了高达98％ee。可以耐受各种N保护基，例如苄基，苯甲基，Boc和PMP。
• Synthesis of Polyheterocyclic Pyrrolo[3,4-b]pyridin-5-ones via a One-Pot (Ugi-3CR/aza Diels-Alder/N-acylation/aromatization/SN2) Process. A Suitable Alternative towards Novel Aza-Analogues of Falipamil
  作者：Angel Zamudio-Medina、Ailyn García-González、Genesis Herrera-Carrillo、Daniel Zárate-Zárate、Adriana Benavides-Macías、Joaquín Tamariz、Ilich Ibarra、Alejandro Islas-Jácome、Eduardo González-Zamora

  DOI：10.3390/molecules23040763

  日期：——

  We describe the one-pot synthesis of twenty polyheterocyclic pyrrolo[3,4-b]pyridin-5-ones via a cascade process (Ugi-3CR/aza Diels-Alder/N-acylation/aromatization) in 20 to 95% overall yields, as well as four pharmacologically promising analogues via an improved cascade process (Ugi-3CR/aza Diels-Alder/N-acylation/aromatization/SN2): two piperazine-linked pyrrolo[3,4-b]pyridin-5-ones in 33 and 34%

  我们描述了通过级联过程（Ugi-3CR / Aza Diels-Alder / N-酰化/芳构化）以20％至95％的总产率一锅合成二十个多杂环吡咯并[3,4-b]吡啶基-5-酮，以及通过改进的级联过程（Ugi-3CR / Aza Diels-Alder / N-酰化/芳香化/ SN2）得到的四个在药理上有希望的类似物：两个哌嗪连接的吡咯并[3,4-b]吡啶-5-酮33％和34％，以及几个Falipamil氮杂类似物，总产率为30％和35％。值得一提的是，发现了良好的底物范围，因为最终产品配有烷基，芳基和杂环取代基。使用链环可互变异构异氰酸酯（作为Ugi型三组分反应的关键试剂）可以快速有效地组装多取代的羟吲哚，这些化合物原位用于复杂的产品，
• Manganese(III) Porphyrin‐Catalyzed Dehydrogenation of Alcohols to form Imines, Tertiary Amines and Quinolines
  作者：Kobra Azizi、Sedigheh Akrami、Robert Madsen

  DOI：10.1002/chem.201900737

  日期：2019.5.2

  Manganese(III) porphyrin chloride complexes have been developed for the first time as catalysts for the acceptorless dehydrogenative coupling of alcohols and amines. The reaction has been applied to the direct synthesis of imines, tertiary amines and quinolines where only hydrogen gas and/or water are formed as the by‐product(s). The mechanism is believed to involve the formation of a manganese(III) alkoxide

  锰（III）卟啉氯化物络合物首次被开发为用于醇和胺的无受体脱氢偶联的催化剂。该反应已应用于亚胺，叔胺和喹啉的直接合成，其中仅形成氢气和/或水作为副产物。据信该机理涉及形成锰（III）醇盐配合物，该配合物降解为醛和氢化锰（III）物质。后者与醇反应形成氢气，从而再生醇盐配合物。
• Cp*Ir complex bearing a flexible bridging and functional 2,2′-methylenebibenzimidazole ligand as an auto-tandem catalyst for the synthesis of N-methyl tertiary amines from imines via transfer hydrogenation/N-methylation with methanol
  作者：Xiaozhong Chen、Yao Ai、Peng Liu、Chenchen Yang、Jiazhi Yang、Feng Li

  DOI：10.1016/j.jcat.2021.08.037

  日期：2021.10

  A Cp*Ir complex bearing a flexible bridging and functional 2,2′-methylenebibenzimidazole ligand was designed, synthesized, and found to be a general and efficient auto-tandem catalyst for the synthesis of N-methyl tertiary amines from imines via transfer hydrogenation/N-methylation with methanol as both hydrogen source and methylating reagent. In the presence of [Cp*Ir(2,2′-CH2BiBzImH2)Cl][Cl], a range

  设计、合成了带有柔性桥接和功能性 2,2'-亚甲基联苯并咪唑配体的 Cp*Ir 配合物，并发现它是一种通用且高效的自串联催化剂，用于通过转移氢化从亚胺合成 N-甲基叔胺/N-甲基化用甲醇作为氢源和甲基化试剂。在 [Cp*Ir(2,2'-CH 2 BiBzImH 2 )Cl][Cl] 存在下，以高收率和几乎完全的选择性获得了一系列理想的产物。由于高度的原子经济性以及最少的化学品和能源消耗，该反应极具吸引力。值得注意的是，这项研究展示了金属-配体双功能催化剂在活化甲醇作为有机合成的 C1 来源方面的新潜力。
• Ligandless Nickel-Catalyzed <i>Ortho</i>-Selective Directed Trifluoromethylthiolation of Aryl Chlorides and Bromides Using AgSCF₃
  作者：Tin Nguyen、Weiling Chiu、Xinying Wang、Madeleine O. Sattler、Jennifer A. Love

  DOI：10.1021/acs.orglett.6b02689

  日期：2016.11.4

  A mild protocol for Ni-catalyzed trifluoromethylthiolation of aryl chlorides and bromides is described herein. The method utilizes AgSCF3 as an easily accessible nucleophilic trifluoromethylthiolating reagent and does not require any ligands or additives. Ortho-selectivity is achieved using a variety of directing groups such as imines, pyridines, and oxazolines for 24 examples in up to 95% yield.

  本文描述了Ni催化的芳基氯化物和溴化物的三氟甲基硫醇化的温和方案。该方法利用AgSCF 3作为容易获得的亲核三氟甲基硫醇化试剂，不需要任何配体或添加剂。对于24个实例，使用多种指导基团如亚胺，吡啶和恶唑啉实现邻位选择性，产率高达95％。