6,7-dimethoxy-1-methylene-3,4-dihydro-1H-isoquinoline-2-carbaldehyde | 154013-14-6

• 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: 6,7-dimethoxy-1-methylene-3,4-dihydro-1H-isoquinoline-2-carbaldehyde
• 英文别名: 2-Formyl-6,7-dimethoxy-1-methylene-1,2,3,4-tetrahydroisoquinoline；6,7-dimethoxy-1-methylene-3,4-dihydroisoquinoline-2(1H)-carbaldehyde；6,7-dimethoxy-1-methylidene-3,4-dihydroisoquinoline-2-carbaldehyde
• CAS: 154013-14-6
• 化学式: C₁₃H₁₅NO₃
• 分子量: 233.267
• InChiKey: UTOXFLBONJNJPN-UHFFFAOYSA-N

物化性质

• 熔点：
  135-137 °C
• 沸点：
  430.1±45.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6,7-dimethoxy-1-methylene-3,4-dihydro-1H-isoquinoline-2-carbaldehyde 在 polyphophoric acid 作用下， 生成 1-甲基-6,7-二甲氧基-3,4-二氢异喹啉
  参考文献：
  名称：

  A Synthesis of N-Formylenamides of Isoquinoline

  摘要：

  N-Formylenamides of isoquinoline (6) were obtained from N-[2-(2-acyl-4,5 -dimethoxyphenyl)ethyl] formamides (5) by cyclization in the presence of catalytic amount of p-toluensulfonic acid. The starting keto formamides (5) were obtained by acylation of a N-[2-(3,4-dimethoxyphenyl)ethyl] formam ides (1) with carboxylic acids or their anhydrides in polyphosphoric acid (PPA).

  DOI：

  10.3987/com-05-10645
• 作为产物：
  描述：

  N-(3,4-二甲氧基苯乙基)甲酰胺 在 PPA 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 2.5h， 生成 6,7-dimethoxy-1-methylene-3,4-dihydro-1H-isoquinoline-2-carbaldehyde
  参考文献：
  名称：

  A Synthesis of N-Formylenamides of Isoquinoline

  摘要：

  N-Formylenamides of isoquinoline (6) were obtained from N-[2-(2-acyl-4,5 -dimethoxyphenyl)ethyl] formamides (5) by cyclization in the presence of catalytic amount of p-toluensulfonic acid. The starting keto formamides (5) were obtained by acylation of a N-[2-(3,4-dimethoxyphenyl)ethyl] formam ides (1) with carboxylic acids or their anhydrides in polyphosphoric acid (PPA).

  DOI：

  10.3987/com-05-10645

文献信息

• General asymmetric synthesis of isoquinoline alkaloids. Enantioselective hydrogenation of enamides catalyzed by BINAP-ruthenium(II) complexes
  作者：Masato Kitamura、Yi Hsiao、Masako Ohta、Masaki Tsukamoto、Tetsuo Ohta、Hidemasa Takaya、Ryoji Noyori

  DOI：10.1021/jo00081a007

  日期：1994.1

  In the presence of a small amount of RuX(2)[(R)- or (S)-BINAP] (X = anionic ligand) a wide range of (Z)-2-acyl-1-benzylidene-1,2,3,4-tetrahydroisoquinolines are hydrogenated to give the saturated products in nearly quantitative yields and in high (up to 100 %) optical yields. The enamide substrates are selectively prepared by N-acylation of the corresponding 1-benzylated 3,4-dihydroisoquinolines under suitable acylation conditions; some crystalline materials having low solubility are obtained by a second-order Z/E stereomutation technique utilizing the double-bond photolability and lattice energy effects. This asymmetric hydrogenation sets the key stereogenic center in a predictable manner, either R or S flexibly, at the C(1) position of the benzylated tetrahydroisoquinolines. The chiral products are converted by standard functional group modification to tetrahydropapaverine, laudanosine, tretoquinol, norreticuline, etc. Hydrogenation of the simple 1-methylene substrate is used fbr synthesis of salsolidine. This enantioselective hydrogenation is applied to the synthesis of morphine and its artificial analogues such as morphinans and benzomorphans of either chirality. A mnemonic device is presented for predicting the reactivity and enantiofacial selection of the BINAP-Ru catalyzed hydrogenation. Reaction with BINAP-Rh catalyst proceeds with a lower enantioselectivity and an opposite sense of asymmetric induction.
• Mechanism of catalytic asymmetric hydrogenation of 2-formyl-1-methylene-1,2,3,4-tetrahydroisoquinoline using Ru(CH3COO)2[(S)-binap]
  作者：Masaki Tsukamoto、Masahiro Yoshimura、Kazuomi Tsuda、Masato Kitamura

  DOI：10.1016/j.tet.2006.03.055

  日期：2006.6

  The mechanism of the asymmetric hydrogenation of 2-acyl-1-alkylidene-1,2,3,4-tetrahydroisoquinolines, the first reported reaction with the Noyori-Takaya Ru(CH3COO)(2)(binap) complex, has been investigated by means of deuterium labeling, kinetics, and NMR analysis. A series of experiments has revealed that (1) a monohydride-unsaturated mechanism operates involving the initial formation of RuH followed by reaction with the enamide substrate, (2) the hydride transfer from RuH to the olefinic double bond is endothermic and reversible, and (3) the rate is determined in the hydrogenolysis step. This view is consistent with that of proposed for the BINAP-Ru catalyzed Kagan reaction. (c) 2006 Elsevier Ltd. All rights reserved.
• A Synthesis of N-Formylenamides of Isoquinoline
  作者：Iliyan Ivanov、Stoyanka Nikolova、Stela Statkova-Abeghe、Plamen Angelov

  DOI：10.3987/com-05-10645

  日期：——

  N-Formylenamides of isoquinoline (6) were obtained from N-[2-(2-acyl-4,5 -dimethoxyphenyl)ethyl] formamides (5) by cyclization in the presence of catalytic amount of p-toluensulfonic acid. The starting keto formamides (5) were obtained by acylation of a N-[2-(3,4-dimethoxyphenyl)ethyl] formam ides (1) with carboxylic acids or their anhydrides in polyphosphoric acid (PPA).

表征谱图