2-methyl-1-phenyl-1,2,3,4-tetrahydroisoquinoline | 7149-64-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢异喹啉
• 英文名称: 2-methyl-1-phenyl-1,2,3,4-tetrahydroisoquinoline
• 英文别名: N-methyl-1-phenyl-1,2,3,4-tetrahydroisoquinoline；2-methyl-1-phenyl-1,2,3,4-tetrahydro-isoquinoline；2-Methyl-1-phenyl-1,2,3,4-tetrahydro-isochinolin；2-methyl-1-phenyl-3,4-dihydro-1H-isoquinoline
• CAS: 7149-64-6
• 化学式: C₁₆H₁₇N
• 分子量: 223.318
• InChiKey: MKANNBGMJZQSFY-UHFFFAOYSA-N

物化性质

• 沸点：
  321.2±11.0 °C(Predicted)
• 密度：
  1.055±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methyl-1-phenyl-1,2,3,4-tetrahydroisoquinoline 在 N-溴代丁二酰亚胺(NBS) 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 sodium carbonate 、 (S)-(-)-[(5,6),(5',6')-双(乙烯二氧)联苯-2,2'-基]二苯基磷 、 氢气 作用下， 以 1,2-二氯乙烷 为溶剂， 20.0~30.0 ℃ 、3.45 MPa 条件下， 反应 24.33h， 以92%的产率得到(R)-2-methyl-1-phenyl-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  Concise Redox Deracemization of Secondary and Tertiary Amines with a Tetrahydroisoquinoline Core via a Nonenzymatic Process

  摘要：

  A concise deracemization of racemic secondary and tertiary amines with a tetrahydroisoquinoline core has been successfully realized by orchestrating a redox process consisted of N-bromosuccinimide oxidation and iridum-catalyzed asymmetric hydrogenation. This compatible redox combination enables one-pot, single-operation deracemization to generate chiral 1-substituted 1,2,3,4-tetrahydroisoquinolines with up to 98% ee in 93% yield, offering a simple and scalable synthetic technique for chiral amines directly from racemic starting materials.

  DOI：

  10.1021/jacs.5b06659
• 作为产物：
  描述：

  2-methyl-1-phenyl-1,2-dihydroisoquinoline 在 乙醇 、 sodium 作用下， 生成 2-methyl-1-phenyl-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  Medical Career Choices: Traditional and New Possibilities

  摘要：

  DOI：

  10.1001/jama.285.17.2249

文献信息

• Contra-thermodynamic Hydrogen Atom Abstraction in the Selective C–H Functionalization of Trialkylamine <i>N</i>-CH₃ Groups
  作者：Joshua P. Barham、Matthew P. John、John A. Murphy

  DOI：10.1021/jacs.6b09690

  日期：2016.11.30

  high selectivity over N-CH2R or N-CHR2 groups. The radical cation DABCO+•, prepared in situ by oxidation of DABCO with a triarylaminium salt, effects highly selective and contra-thermodynamic C-H abstraction from N-CH3 groups. The intermediates that result react in situ with organometallic nucleophiles in a single pot, affording novel and highly selective homologation of N-CH3 groups. Chemoselectivity

  我们报告了一个简单的一锅法，它提供了 N-甲基-N,N-二烷基胺中 N-CH3 基团的功能化，对 N-CH2R 或 N-CHR2 基团具有高选择性。通过用三芳基胺盐氧化 DABCO 原位制备的自由基阳离子 DABCO+• 从 N-CH3 基团中影响高选择性和逆热力学 CH 提取。产生的中间体在一个锅中与有机金属亲核试剂原位反应，提供新的和高度选择性的 N-CH3 基团同系化。证明了试剂的化学选择性、可扩展性和可回收性，并通过计算和实验结果证实了机制建议。转化的效用在天然产物和药物的后期位点选择性功能化中得到证明，
• Phencyclidine-like effects of tetrahydroisoquinolines and related compounds
  作者：Nancy M. Gray、Brian K. Cheng、Stephen J. Mick、Cecelia M. Lair、Patricia C. Contreras

  DOI：10.1021/jm00126a016

  日期：1989.6

  3-c]pyridines, and related compounds were evaluated for their ability to inhibit binding of [3H]-1-[1-(2-thienyl)piperidine and [3H]-N-allylnormetazocine to phencyclidine (PCP) and sigma receptors, respectively. A representative series of compounds was evaluated in behavioral assays to determine the ability of the compounds to induce PCP-like stereotyped behavior and ataxia. All of the compounds caused stereotyped

  评价了一系列1,2,3,4-四氢异喹啉，四氢噻吩并[2,3-c]吡啶和相关化合物抑制[3H] -1- [1-（2-噻吩基）哌啶结合的能力和[3H] -N-烯丙基谷氨酸对苯环利定（PCP）和sigma受体的影响。在行为测定中评估了一系列代表性化合物，以确定这些化合物诱导PCP样​​定型行为和共济失调的能力。所有这些化合物均引起定型行为和共济失调，表明它们在PCP部位具有激动作用。
• One-pot functionalisation of <i>N</i>-substituted tetrahydroisoquinolines by photooxidation and tunable organometallic trapping of iminium intermediates
  作者：Joshua P Barham、Matthew P John、John A Murphy

  DOI：10.3762/bjoc.10.316

  日期：——

  stabilised carbon nucleophiles. The few reports of organometallic additions have limited scope of substrate and organometallic nucleophile. We report a novel, one-pot methodology that functionalises N-substituted tetrahydroisoquinolines by visible light-assisted photooxidation, followed by trapping of the resultant iminium ions with organometallic nucleophiles. This affords 1,2-disubstituted tetrahydroisoquinolines

  通过稳定的碳亲核试剂已经很好地确立了通过叔胺的氧化功能化生成的亚胺盐的亲核捕获。关于有机金属添加物的报道很少，限制了底物和有机金属亲核试剂的范围。我们报告了一种新颖的一锅法，通过可见光辅助的光氧化功能化N-取代的四氢异喹啉，然后用有机金属亲核试剂捕获所得的亚胺离子。这以中等至优异的产率提供了1，2-二取代的四氢异喹啉。
• 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。
• A New Method of α-Functionalization for Tertiary Amines by Nucleophilic Substitution of α-Siloxy Amines
  作者：Norihiro Tokitoh、Renji Okazaki

  DOI：10.1246/bcsj.61.735

  日期：1988.3

  α-Siloxy amines, which were easily prepared by “silicon Polonovski reaction” of tertiary amine N-oxides with trialkylsilyl trifluoromethanesulfonate, were treated with various nucleophiles to give the corresponding α-functionalized tertiary amines in moderate to good yields. This new method has the advantage that it enables the α-substitution of amines not only by alkyl groups but also by alkenyl and

  α-甲硅烷氧基胺很容易通过叔胺 N-氧化物与三氟甲磺酸三烷基甲硅烷基酯的“硅波洛诺夫斯基反应”制备，用各种亲核试剂处理，以中等至良好的产率得到相应的 α-官能化叔胺。这种新方法的优点是，它不仅可以通过烷基，而且可以通过以 sp2 碳为反应中心的烯基和芳基对胺进行 α 取代，因为在偶极稳定的亲电取代中引入这些基团是困难的。 α-锂硫胺。除了有机金属化合物如格氏试剂和有机铝试剂外，三甲基氰化甲硅烷和甲硅烷基烯醇醚也可以在适当的路易斯酸存在下用作亲核试剂。