(+/-)-carnegine | 490-53-9

• 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: (+/-)-carnegine
• 英文别名: 6,7-Dimethoxy-1,2-dimethyl-1,2,3,4-tetrahydroisoquinoline；(±)-carnegine；Carnegine；6,7-dimethoxy-1,2-dimethyl-1,2,3,4-tetrahydro-isoquinoline；(+/-)-6,7-dimethoxy-1,2-dimethyl-1,2,3,4-tetrahydro-isoquinoline；(+/-)-6,7-Dimethoxy-1,2-dimethyl-1,2,3,4-tetrahydro-isochinolin；6,7-dimethoxy-1,2-dimethyl-3,4-dihydro-1H-isoquinoline
• CAS: 490-53-9
• 化学式: C₁₃H₁₉NO₂
• 分子量: 221.299
• InChiKey: HRSIPKSSEVRSPG-UHFFFAOYSA-N

物化性质

• 熔点：
  <25 °C
• 沸点：
  362.36°C (rough estimate)
• 密度：
  1.0451 (rough estimate)
• 保留指数：
  1727

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.538
• 拓扑面积：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-carnegine 在 D-酒石酸 、 氨 作用下， 以 水 为溶剂， 生成 (S)-(-)-carnegine
  参考文献：
  名称：

  Online Structural Elucidation of Alkaloids and Other Constituents in Crude Extracts and Cultured Cells of Nandina domestica by Combination of LC-MS/MS, LC-NMR, and LC-CD Analyses

  摘要：

  The combination of NMR, MS, and CD data permitted the structural elucidation including the absolute configuration of the known alkaloids and unknown components in the extract matrix solution of Nandina domestica without isolation and sample purification prior to the coupling experiments. Unstable natural stereoisomers were identified by LC-NMR and LC-MS. Five known alkaloids, (S)-isoboldine, (S)-domesticine, (S)-nantenine, sinoacutine, and menispermine, were identified from N. domestica. O-Methylpallidine and (E,E)-. (E,Z)-, and (Z,Z)-terrestribisamide were also characterized for the first time from this plant. Known jatrorrhizine, palmatine, and berberine and unknown (R)-carnegine and (E.E)-, (E,Z)-, and (Z,Z)-terrestribisamide were identified in the callus of N. domestica.

  DOI：

  10.1021/np8001496
• 作为产物：
  描述：

  6,7-二甲氧基异喹啉 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 生成 (+/-)-carnegine
  参考文献：
  名称：

  Isoquinoline-N-boranes as precursors to substituted tetrahydroisoquinolines

  摘要：

  DOI：

  10.1021/jo00175a027

文献信息

• Transfer Hydrogenation of Isoquinolinium Salts Catalyzed by a Rhodium Complex
  作者：Jin Zhu、Jingen Deng、Jiashou Wu、Jian Liao

  DOI：10.1055/s-2006-949606

  日期：2006.8

  Regio- and chemoselective transfer hydrogenation of isoquinolinium salts catalyzed by [Cp*RhCl2]2 using HCOOH-Et3N (5:2) as a hydrogen source was realized. A variety of N-methyl- and N-benzyl-1,2,3,4-tetrahydroisoquinoline alkaloids were obtained in high yields by the present catalyst system.

  使用HCOOH-Et3N (5:2)作为氢源，以[Cp*RhCl2]2为催化剂，实现了对异喹啉盐的区域和化学选择性转移氢化。通过该催化体系获得了多种高产率的N-甲基和N-苄基-1,2,3,4-四氢异喹啉生物碱。
• Indium metal as a reducing agent in organic synthesis
  作者：Michael R. Pitts、Justin R. Harrison、Christopher J. Moody

  DOI：10.1039/b101712h

  日期：——

  aromatic nitro compounds under similar conditions results in selective reduction of the nitro groups; ester, nitrile, amide and halide substituents are unaffected. Likewise indium in aqueous ethanolic ammonium chloride is an effective method for the deprotection of 4-nitrobenzyl ethers and esters. Indium is also an effective reducing agent under non-aqueous conditions and α-oximino carbonyl compounds can

  铟的低第一电离能（5.8 eV）及其对空气和水的稳定性表明，这种金属元素应是有机基材的有用还原剂。使用铟金属还原C描述了肟，硝基化合物和共轭烯烃的亚胺中的N键，苯并稠合的氮杂环中的杂环以及4-硝基苄基保护基的去除。因此，使用乙醇氯化铵水溶液中的铟金属选择性地还原喹啉，异喹啉和喹喔啉中的杂环。在相似条件下处理一系列芳香族硝基化合物会导致硝基的选择性还原；酯，腈，酰胺和卤化物取代基不受影响。同样地，乙醇乙醇铵水溶液中的铟是使4-硝基苄基醚和酯脱保护的有效方法。铟在非水条件下也是有效的还原剂，α-肟基羰基化合物可以选择性地还原为相应的N-在乙酸酐或二碳酸二叔丁酯存在下，用铟粉，乙酸在THF中的叔胺保护。在THF-乙酸中的铟也会还原共轭烯烃。
• Structure and Biocatalytic Scope of Coclaurine <i>N</i> ‐Methyltransferase
  作者：Matthew R. Bennett、Mark L. Thompson、Sarah A. Shepherd、Mark S. Dunstan、Abigail J. Herbert、Duncan R. M. Smith、Victoria A. Cronin、Binuraj R. K. Menon、Colin Levy、Jason Micklefield

  DOI：10.1002/anie.201805060

  日期：2018.8.13

  plant secondary metabolites, which have been exploited to develop analgesics, antibiotics, antitumor agents, and other therapeutic agents. Biosynthesis of BIAs proceeds via a common pathway from tyrosine to (S)‐reticulene at which point the pathway diverges. Coclaurine N‐methyltransferase (CNMT) is a key enzyme in the pathway to (S)‐reticulene, installing the N‐methyl substituent that is essential for

  苄基异喹啉生物碱 (BIA) 是结构多样的植物次生代谢物家族，已被用来开发镇痛药、抗生素、抗肿瘤剂和其他治疗剂。BIA 的生物合成通过从酪氨酸到 ( S )-网状荠烯的共同途径进行，此时该途径出现分歧。椰壳碱N-甲基转移酶 (CNMT) 是 ( S )-网状荠烯途径中的关键酶，安装N-甲基取代基，这对于许多 BIA 的生物活性至关重要。在本文中，我们描述了 CNMT 的第一个晶体结构，它与诱变研究一起定义了酶活性位点的结构。还利用一系列天然和合成底物以及辅因子类似物探索了 CNMT 的特异性。这项研究的知识可用于生成生产 BIA 或合成衍生物所需的改进 CNMT 变体。
• Synthesis of 1-Substituted Tetrahydroisoquinolines by Lithiation and Electrophilic Quenching Guided by In Situ IR and NMR Spectroscopy and Application to the Synthesis of Salsolidine, Carnegine and Laudanosine
  作者：Xiabing Li、Daniele Leonori、Nadeem S. Sheikh、Iain Coldham

  DOI：10.1002/chem.201301096

  日期：2013.6.10

  The lithiation of N‐tert‐butoxycarbonyl (N‐Boc)‐1,2,3,4‐tetrahydroisoquinoline was optimized by in situ IR (ReactIR) spectroscopy. Optimum conditions were found by using n‐butyllithium in THF at −50 °C for less than 5 min. The intermediate organolithium was quenched with electrophiles to give 1‐substituted 1,2,3,4‐tetrahydroisoquinolines. Monitoring the lithiation by IR or NMR spectroscopy showed that

  的锂化ñ -叔丁氧羰基（Ñ -Boc）-1,2,3,4-四氢异喹啉用原位IR（的ReactIR）光谱进行了优化。通过在-50°C下于THF中使用正丁基锂少于5分钟发现了最佳条件。用亲电子试剂淬灭中间体有机锂，得到1-取代的1,2,3,4-四氢异喹啉。通过IR或NMR光谱监测锂化表明，一个旋转异构体反应迅速，并且通过可变温度NMR光谱确定了Boc基团的旋转势垒，发现其约为60.8 kJ mol -1，相当于在−50°C下旋转约30 s的半衰期。（-）-天冬氨酸作为配体的使用在亲电淬灭后导致低水平的对映选择性，“穷人霍夫曼试验”表明有机锂在构型上不稳定。该化学方法应用于N -Boc-6,7-二甲氧基-1,2,3,4-四氢异喹啉，并导致外消旋生物碱salsolidine，carnegine，norlaudanosine和laudanosine的有效合成。
• Synthesis of isoquinolines from 2-phenylethylamines, amides, nitriles and carboxylic acids in polyphosphoric acid
  作者：Atanas P. Venkov、Ilian I. Ivanov

  DOI：10.1016/0040-4020(96)00716-8

  日期：1996.9

  A convenient one pot synthesis of 1-. 1.3-substituted 3.4-dihydroisoquinolines 5. enamines 10 and 3-oxo-2,3-dihydroisoquinolines 18 as well as of enamides 22 of isoquinoline from 2-phenyl-. 1,2-diphenylethylamines, phenylacetamides, phenylacetonitriles, N-acylphenylethyl-amines and carboxylic acids in nonaqueous media has been accomplished.

  方便的一锅合成1-。1.3-取代的3.4-二氢异喹啉5。烯胺10和3-氧代-2，3-二氢异喹啉18以及2-苯基-异喹啉的酰胺22。非水介质中的1,2-二苯乙胺，苯乙酰胺，苯乙腈，N-酰基苯乙胺和羧酸已经完成。

表征谱图