(S)-3,4,5,6,7,8-六氢-1-[(4-甲氧基苯基)甲基](1H)-异喹啉-2-甲醛 | 29144-31-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 中文名称: (S)-3,4,5,6,7,8-六氢-1-[(4-甲氧基苯基)甲基](1H)-异喹啉-2-甲醛
• 英文名称: (S)-2-formyl-1-(4-methoxybenzyl)-1,2,3,4,5,6,7,8-octahydroisoquinoline
• 英文别名: (S)-2-Formyl-1-<(4-methoxyphenyl)methyl>-1,2,3,4,5,6,7,8-octahydroispquinoline；(+)-1-(p-methoxybenzyl)-2-formyl-1,2,3,4,5,6,7,8-octahydroisoquinoline；(S)-(+)-N-formyl-1-(p-methoxybenzyl)-1,2,3,4,5,6,7,8-octahydroisoquinoline；(+)-N-formyl octabase；(S)-3,4,5,6,7,8-Hexahydro-1-[(4-methoxyphenyl)methyl](1H)-isoquinoline-2-carbaldehyde；(1S)-1-[(4-methoxyphenyl)methyl]-3,4,5,6,7,8-hexahydro-1H-isoquinoline-2-carbaldehyde
• CAS: 29144-31-8
• 化学式: C₁₈H₂₃NO₂
• 分子量: 285.386
• InChiKey: XSOPBBOEINVWML-SFHVURJKSA-N

物化性质

• 沸点：
  466.8±38.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)
• 溶解度：
  氯仿（少量溶解）、DMSO（少量溶解）、乙酸乙酯（少量溶解）、甲醇（少量溶解）

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2933499090

反应信息

• 作为反应物：
  描述：

  (S)-3,4,5,6,7,8-六氢-1-[(4-甲氧基苯基)甲基](1H)-异喹啉-2-甲醛 在 sodium hydroxide 、 甲酸 、 superphosphoric acid 、 氢溴酸 作用下， 反应 372.0h， 生成 左啡诺
  参考文献：
  名称：

  Passarotti; Valenti; Grianti, Bollettino Chimico Farmaceutico, 1993, vol. 132, # 11, p. 475 - 477

  摘要：

  DOI：
• 作为产物：
  描述：

  N-[2-(1,1-环己烯基)-乙基]-4-甲氧基苯基乙酰胺 在 Ru(OCOCF₃)2((S)-tolbinap) 氢气 、 三氯氧磷 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 苯 为溶剂， 30.0 ℃ 、10.13 MPa 条件下， 反应 108.0h， 生成 (S)-3,4,5,6,7,8-六氢-1-[(4-甲氧基苯基)甲基](1H)-异喹啉-2-甲醛
  参考文献：
  名称：

  General asymmetric synthesis of benzomorphans and morphinans via enantioselective hydrogenation

  摘要：

  DOI：

  10.1016/s0040-4039(00)96636-x

文献信息

• [EN] COMPOSITIONS AND METHODS FOR THE TREATMENT OF RESPIRATORY DISORDERS<br/>[FR] COMPOSITIONS ET MÉTHODES DE TRAITEMENT DE TROUBLES RESPIRATOIRES
  申请人：KANDULA MAHESH

  公开号：WO2013168012A1

  公开（公告）日：2013-11-14

  The invention relates to the compounds of formula (I) or its pharmaceutical acceptable salts, as well as polymorphs, solvates, enantiomers, stereoisomers and hydrates thereof. The pharmaceutical compositions comprising an effective amount of compounds of formula (I), and methods for the treatment of respiratory disorders may be formulated for oral, buccal, rectal, topical, transdermal, transmucosal, intravenous, parenteral administration, syrup, or injection. Such compositions may be used to treatment of cough caused by minor throat and bronchial irritation (such as commonly accompanies the flu and common cold), as well as those resulting from inhaled particle irritants, upper respiratory infections, (pseudobulbar affect) in patients with amyotrophic lateral sclerosis and multiple sclerosis, neuropathic pain and pain associated with fibromyalgia.

  本发明涉及公式(I)化合物或其药用可接受盐，以及它们的聚合物、溶剂化物、对映异构体、立体异构体和水合物。包含有效量的公式(I)化合物的药物组合物，以及用于治疗呼吸系统疾病的方法，可以口服、颊部、直肠、局部、经皮、经粘膜、静脉、非肠道给药、糖浆或注射的剂型。此类组合物可用于治疗由小喉咙和支气管刺激引起的咳嗽（如通常伴随流感和普通感冒），以及由吸入颗粒刺激物、上呼吸道感染、肌萎缩侧索硬化症和多发症患者的（假性球麻痹）以及神经性疼痛和纤维肌痛相关的疼痛。
• On the formation of a side product with hexahydroaporphine-like structure in the Grewe cyclization of dextromethorphan
  作者：Qiao Zhao、Kai Zhao、Sheng-ying Wu、Bo-xue Tian、Leif A. Eriksson、Li-min Wang、Na An、Zhong-zhu Long、Shui-hong Cai

  DOI：10.1007/s11164-016-2723-4

  日期：2017.3

  Factors leading to the formation of a hexahydroaporphine-like cyclizing side product were studied systematically for the first time and the ratio of this side product was controlled effectively. To understand better the electronic effect of substrates on the formation of side products, different 1-benzyloctahydroisoquinolines with substituted groups on nitrogen or benzene ring were compared. A plausible mechanism of cyclizing reaction was proposed, and key intermediates as well as transition states were analyzed using DFT calculations.

  研究人员首次系统地研究了导致形成类似六氢吗啡环化副产物的因素，并有效地控制了这种副产物的比例。为了更好地理解底物对副产物形成的电子效应，比较了氮或苯环上有取代基团的不同 1-苄基八氢异喹啉。研究人员提出了环化反应的合理机理，并利用 DFT 计算分析了关键的中间产物和过渡态。
• 一种右美沙芬中间体的合成方法
  申请人：华东理工大学

  公开号：CN104761496B

  公开（公告）日：2017-05-24

  一种式(I)所示的右美沙芬中间体的制备方法，包括：在惰性溶剂中，稀土路易斯酸催化的条件下，(+)‑N‑酰基‑1‑(4‑甲氧基)苄基‑1,2,3,4,5,6,7,8‑八氢异喹啉化合物进行环合反应得到式(I)所示的(+)‑3‑甲氧基‑17‑酰基吗喃化合物，其中R为C1–C3烷酰基、C1–C3含氧烷酰基、C1–C3含氟烷酰基、C1–C3含氯烷酰基、C1–C3磺酰基或C1–C3含氟磺酰基。本发明的优点是以(+)‑N‑酰基‑1‑(4‑甲氧基)苄基‑1,2,3,4,5,6,7,8‑八氢异喹啉作为环合反应前的底物，在较低温度下实现原料高效转化从而降低能耗；环合剂选自稀土路易斯酸，避免强质子酸对设备腐蚀，减少了三废的排放；环合反应中的副产物明显降低；所用的稀土路易斯酸为催化量，降低生产成本。
• An asymmetric synthesis of (+)-morphinans in high enantiomeric purity
  作者：A. I. Meyers、Thomas R. Bailey

  DOI：10.1021/jo00356a023

  日期：1986.3
• 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.