4-methyl-1,2-dihydroquinoline | 22514-60-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 4-methyl-1,2-dihydroquinoline
• 英文别名: 1,2-dihydrolepidine；4-methyl-1,2-dihydro-quinoline；4-Methyl-1,2-dihydro-chinolin；1,2-Dihydro-4-methylchinolin
• CAS: 22514-60-9
• 化学式: C₁₀H₁₁N
• mdl: MFCD19217040
• 分子量: 145.204
• InChiKey: RDDXLTPBALMBBI-UHFFFAOYSA-N

物化性质

• 熔点：
  58 °C
• 沸点：
  86-87 °C(Press: 0.2 Torr)
• 密度：
  1.011±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-methyl-1,2-dihydroquinoline 在 吡啶 、 palladium diacetate 、 copper(II) bis(trifluoromethanesulfonate) 、 silver(l) oxide 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 3.5h， 生成 4-Methyl-3-phenylquinoline
  参考文献：
  名称：

  Heteroatom-Guided, Palladium-Catalyzed Regioselective C–H Functionalization in the Synthesis of 3-Arylquinolines

  摘要：

  A new approach for the regioselective functionalization of the C-3-position of quinolines is described. The method utilizes heteroatom guided regioselective C-3 palladation followed by arylation via transmetalation with aryl boronic acids to yield 3-aryl-N-acyl-1,2-dihydroquinolines. In a one-pot sequence, N-deacylation followed by aromatization leads to important 3-arylquinolines in good yields.

  DOI：

  10.1021/ol401349a
• 作为产物：
  描述：

  4-甲基喹啉 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 生成 4-methyl-1,2-dihydroquinoline
  参考文献：
  名称：

  Heteroatom-Guided, Palladium-Catalyzed Regioselective C–H Functionalization in the Synthesis of 3-Arylquinolines

  摘要：

  A new approach for the regioselective functionalization of the C-3-position of quinolines is described. The method utilizes heteroatom guided regioselective C-3 palladation followed by arylation via transmetalation with aryl boronic acids to yield 3-aryl-N-acyl-1,2-dihydroquinolines. In a one-pot sequence, N-deacylation followed by aromatization leads to important 3-arylquinolines in good yields.

  DOI：

  10.1021/ol401349a

文献信息

• Observations on the intramolecular Heck reactions of aromatic chlorides using palladium/imidazolium salts
  作者：Stephen Caddick、William Kofie

  DOI：10.1016/s0040-4039(02)02340-7

  日期：2002.12

  The intramolecular Heck reaction of aromatic amines and ethers using palladium/imidazolium salts is described. The use of tetra-n-butylammonium halide salts facilitates the reactivity of aromatic chlorides. An unexpected and novel palladium-mediated cyclisation is also described leading to the formation of a tricyclic adduct.

  描述了使用钯/咪唑鎓盐的芳族胺和醚的分子内Heck反应。四正丁基卤化铵盐的使用促进了芳族氯化物的反应性。还描述了意外的和新颖的钯介导的环化作用，导致三环加合物的形成。
• Enantioselective Synthesis of 4-Aminotetrahydroquinolines via 1,2-Reductive Dearomatization of Quinolines and Copper(I) Hydride-Catalyzed Asymmetric Hydroamination
  作者：Qing-Feng Xu-Xu、Xiao Zhang、Shu-Li You

  DOI：10.1021/acs.orglett.9b02034

  日期：2019.7.5

  1,2-reductive dearomatization of quinolines and copper(II) acetate monohydrate/(R,R)-Ph-BPE/P(p-tolyl)3-catalyzed enantioselective hydroamination sequence was developed, affording diverse 4-amino-1,2,3,4-tetrahydroquinolines with high levels of enantioselectivity in either a stepwise or one-pot fashion. Pleasingly, internal cis-cyclic alkenes, which are challenging substrates in copper hydride-catalyzed

  开发了喹啉和一水合乙酸铜（II）/（R，R）-Ph-BPE / P（对甲苯基）3-催化的对映选择性加氢胺化反应的1,2-还原脱芳香化反应，提供了多种4-氨基-1，具有高对映选择性的2,3,4-四氢喹啉，呈逐步或一锅方式。令人愉快的是，在氢化铜催化的对映选择性加氢胺化反应中具有挑战性的底物内部顺式环烯烃在温和条件下得到了有效转化。
• Mechanistic Aspects of the Carboxylative Cyclization of Propargylamines and Carbon Dioxide Catalyzed by Gold(I) Complexes Bearing an<i>N</i>-Heterocyclic Carbene Ligand
  作者：Shun Hase、Yoshihito Kayaki、Takao Ikariya

  DOI：10.1021/acscatal.5b01335

  日期：2015.9.4

  introduction of aromatic substituents at the alkyne terminus. The formation of alkenylgold(I) complexes as catalytic intermediate models is demonstrated by the treatment of methyl- and phenyl-substituted propargylamines with AuOH(IPr) under a CO2 atmosphere. A comparison of the reactivity of the alkenylgold(I) complexes clearly indicates that the alkenyl ligand attached to an alkyl group at the α position

  IPr-金（I）（IPr = 1,3-双（2,6-二异丙基苯基）-咪唑-2-亚烷基）配合物可促进使用二氧化碳（CO 2）的一系列炔丙基胺的羧基环化反应，从而制得（Z）-5-亚烷基-2-恶唑烷酮在甲醇中，在温和的条件下，即使在没有添加剂（如银盐和碱）的情况下也是如此。对底物范围的研究表明，由于炔烃末端引入芳族取代基，催化性能显着降低。alkenylgold的形成（I）配合物作为催化剂的中间模型是通过甲基的治疗和苯基取代的炔丙胺与AuOH（IPR）一个CO下表现出2气氛。烯基金（I）配合物的反应性的比较清楚地表明，与在苯基上连接的烯基配体相比，在α位的烷基上连接的烯基配体更易于质子分解。这些结果和动力学实验证实了催化循环，该循环涉及氨基甲酸酯在与Au中心键合的C–C三键上的亲核攻击，以及随后的原型脱氢反应，以释放出环状氨基甲酸酯产物。
• Enantioselective Synthesis of Boryl Tetrahydroquinolines via Cu-Catalyzed Hydroboration
  作者：Duanyang Kong、Suna Han、Guofu Zi、Guohua Hou、Jiaxin Zhang

  DOI：10.1021/acs.joc.7b02860

  日期：2018.2.16

  A Cu-catalyzed regio- and enantioselective hydroboration of 1,2-dihydroquinolines with high yields and excellent enantioselectivities (up to 98% ee) was presented. This method could be applied in the asymmetric synthesis of the important intermediates used in the enantioselective synthesis of the potential agent Sumanirole for the treatment of Parkinson’s disease and of the potentially interesting

  提出了Cu催化的1，2-二氢喹啉区域和对映体选择性硼氢化，具有高收率和优异的对映选择性（高达98％ee）。该方法能够在潜在剂Sumanirole的对映选择性合成用于和潜在的有趣正性肌力剂（的帕金森氏病的治疗中的重要的中间体的不对称合成可以应用小号- ）903。
• METHOD FOR MANUFACTURING OPTICALLY ACTIVE COMPOUND
  申请人：SUMITOMO CHEMICAL COMPANY, LIMITED

  公开号：US20170022162A1

  公开（公告）日：2017-01-26

  The present invention provides a method for manufacturing an optically active compound of formula (2), which contains bringing hydrogen into contact with a compound of formula (1) in the presence of a transition metal catalyst having an optically active ligand. In the formula, R 1 represents a hydrogen atom or an acetyl group, R 2 , R 3 , R 4 , and R 5 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a nitro group, an amino group, or an acyl group, R 6 represents an alkyl group, R 7 and R 8 each independently represents a hydrogen atom or an alkyl group, and a carbon atom marked with an asterisk (*) represents an asymmetric carbon atom.

  本发明提供了一种制备式（2）的光学活性化合物的方法，其中包括在具有光学活性配体的过渡金属催化剂存在下，将氢与式（1）的化合物接触。在该式中，R1代表氢原子或乙酰基，R2、R3、R4和R5各自独立地代表氢原子、卤素原子、烷基、烷氧基、羟基、硝基、氨基或酰基，R6代表烷基，R7和R8各自独立地代表氢原子或烷基，而用星号（*）标记的碳原子代表一个不对称碳原子。