紫堇沙明碱 | 11028-77-6

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 原小檗碱生物碱及其衍生物
• 中文名称: 紫堇沙明碱
• 英文名称: corysamine chloride
• 英文别名: corysamine；13-methylcoptisine；13-methylcoptisine chloride；24-methyl-5,7,17,19-tetraoxa-13-azoniahexacyclo[11.11.0.02,10.04,8.015,23.016,20]tetracosa-1(13),2,4(8),9,14,16(20),21,23-octaene;chloride
• CAS: 11028-77-6
• 化学式: C₂₀H₁₆NO₄*Cl
• 分子量: 369.804
• InChiKey: WMUNRKMYZOSRSH-UHFFFAOYSA-M

物化性质

• 熔点：
  >290 °C (decomp)

计算性质

• 辛醇/水分配系数(LogP)：
  0.12
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  40.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  紫堇沙明碱 在 sodium tetrahydroborate 、 potassium carbonate 、 sodium hydroxide 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以75.7%的产率得到13-methyldihydrocoptisine
  参考文献：
  名称：

  Derivatives Of Protoberberine Biological Alkaloids And Use Of Same Inhibiting Ulcerative Colitis

  摘要：

  本文披露了通过对原生物碱类季铵盐的源材料进行衍生反应而产生的原生物碱类季铵盐的衍生物或其生理上可接受的盐，以及其制备方法和药用用途。原生物碱类季铵盐的衍生物或其生理上可接受的盐显示出抑制溃疡性结肠炎的活性，并可用于制备相应药物。

  公开号：

  US20150031717A1
• 作为产物：
  描述：

  二氢黄连碱 在 盐酸 作用下， 以 乙醇 、 水 为溶剂， 反应 5.0h， 生成 紫堇沙明碱
  参考文献：
  名称：

  Syntheses and structure–activity relationships in cytotoxicities of 13-substituted quaternary coptisine derivatives

  摘要：

  Twenty five 13-substituted quaternary coptisine derivatives were synthesized to test their cytotoxicities against several cancer cell-lines and on intestinal epithelial cell-6 (IEC-6) in vitro to evaluate structure-activity relationship (SAR). Introduction of the alkyl groups into the C-13 position of quaternary coptisine (1) led to significant increase of the cytotoxic activity, while the substitution of arylmethyl groups and others at the same position showed no effect on improving cytotoxicities against the same cancer cell-lines. The cytotoxicities of quaternary 13-alkylcoptisines was significantly reinforced as the length of the aliphatic chain increased, with quaternary 13-n-undecylcoptisine (4l) showing 7, 23, 12, and 9 times, respectively, more active than quaternary coptisine (1) against HCT, A549, Be17402, and C33A, and being 4, 11, 2, and 3 times, respectively, more active than the positive control, fluorouracil (5-FU), against the same cell-lines, by IC50 values. In comparison to quaternary 13-n-undecylcoptisine (4l) and the above references, quaternary 13-n-dodecylcoptisine (4m) almost showed the same cytotoxicities. In contrast with the n-alkyl chains, the arylmethyl substituents at C-13 displayed low cytotoxicity, except for naphthyl rings or phenyl rings with CF3 or methyl substituents. However, their low cytotoxicity could make them useful as drug candidates for other diseases (bowel, etc). (C) 2014 Elsevier Masson SAS. All rights reserved.

  DOI：

  10.1016/j.ejmech.2014.09.006

文献信息

• Derivatives Of Protoberberine Biological Alkaloids And Use Of Same Inhibiting Ulcerative Colitis
  申请人：Institute of Materia Medica, Chinese Academy of Medical Sciences

  公开号：US20150031717A1

  公开（公告）日：2015-01-29

  Disclosed are derivatives of protoberberine biological alkaloids or physiologically acceptable salts thereof produced by means of a derivative reaction of a source material of biological alkaline quaternary ammonium salts of protoberberine alkaloids, a preparation method for same and pharmaceutical uses thereof. The derivatives of protoberberine biological alkaloids or the physiologically acceptable salts thereof show activity inhibiting ulcerative colitis and can be used in the preparation of drugs for same.

  本文披露了通过对原生物碱类季铵盐的源材料进行衍生反应而产生的原生物碱类季铵盐的衍生物或其生理上可接受的盐，以及其制备方法和药用用途。原生物碱类季铵盐的衍生物或其生理上可接受的盐显示出抑制溃疡性结肠炎的活性，并可用于制备相应药物。
• A novel and efficient synthesis of 13-methylprotoberberine alkaloids
  作者：Miyoji Hanaoka、Shuji Yoshida、Chisato Mukai

  DOI：10.1039/c39850001257

  日期：——

  13-Methylberberine (6a), dehydrocorydaline (6b), and corysamine (6c, and their tetrahydro derivatives (9a–c) were efficiently synthesised from the corresponding protoberberines (1) through photochemical electrocyclic reaction of 13-methylene-8, 14-cycloberbines (3).

  通过相应的原小-8碱（1）通过13-亚甲基-8、14-环小bin碱的光化学环化反应，有效地合成了13-甲基小ber碱（6a），脱氢科达林（6b）和corysamine（6c及其四氢衍生物（9a - c）。（3）。
• Chemical transformation of protoberberines. XV. A novel and efficient method for the introduction of alkyl groups on the C-13 position in the protoberberine skeleton.
  作者：Miyoji HANAOKA、Shuji YOSHIDA、Chisato MUKAI

  DOI：10.1248/cpb.37.3264

  日期：——

  The Wittig reaction of 8, 14-cycloberbin-13-ones (4), derived from the corresponding protoberberine alkaloids (2), with methylenetriphenylphosphorane afforded 13-methylene-8, 14-cycloberbines (5). Irradiation of 5 with a 100 W high pressure mercury lamp effected photochemically-induced electrocyclic fission of the aziridine ring to yield 13-methylberberine (1a), dehydrocorydaline (1b), and corysamine (1c) in high yield. Introduction of ethyl and propyl groups on the C-13 position in 2 was also conveniently achieved via photochemical reaction of the corresponding alkylidene derivatives (8 and 9, respectively).

  8, 14-环贝尔本-13-酮（4）通过与甲烯三苯基膦的维蒂格反应，来自相应的原贝尔巴林生物碱（2），得到13-亚甲基-8, 14-环贝尔本（5）。使用100 W高压汞灯对5进行辐照，促进了光化学诱导的电环裂解，生成高产率的13-甲基贝尔巴林（1a）、去氢可可碱（1b）和可可酸（1c）。通过相应烷基烯烃衍生物（8和9）进行光化学反应，还方便地在2的C-13位引入了乙基和丙基取代基。
• Alkaloids from Corydalis cava (L.) SCHW. et KOERTE
  作者：Jiří Slavík、Leonora Slavíková

  DOI：10.1135/cccc19792261

  日期：——

  From the tubers of Corydalis cava (L.) SCHW. et KOERTE the following alkaloids were isolated: (+)-bulbocapnine, (+)-corydaline, (+)- and (±)-tetrahydropalmatine, (+)- and (±)-thalictricavine, (+)-corybulbine, corycavine, protopine, (+)-corypalmine, (±)- and (+)-isocorypalmine, (+)-corytuberine, (+)-corydine, (+)- and (±)-corycavidine, (+)-canadine, (+)-stylopine, (-)-scoulerine, capnoidine, dehydrocorydaline, corysamine, coptisine; further the following alkaloids not yet described as components of this plant: (+)-tetrahydrocorysamine, allocryptopine, palmatine, berberine, dehydrocorybulbine, dehydrothalictricavine, (+)-α-stylopine methohydroxide and the alkaloid CC2, as well as the new neutral alkaloids dehydroapocavidine, (+)-bulbocapnine methohydroxide, and α-tetrahydrocorysamine methohydroxide. Further the presence of apocavidine, columbamine, jatrorrhizine and magnoflorine was also proved. In the aerial parts (+)-bulbocapnine, (+)-stylopine, protopine, capnoidine, glaucine, domestine alkaloid CC1 (probably dehydrodomestine), predicentrine, isoboldine corydine, coptisine, corysamine and traces of bulbocapnine methohydroxide were found.

  从洼地黄（Corydalis cava）的块茎中分离出以下生物碱：(+)-鼠曲草碱、(+)-洼地黄碱、(+)-和(±)-四氢棕榈碱、(+)-和(±)-洼地黄碱、(+)-洼地黄酮、洼地黄碱、原品、(+)-洼地黄碱、(±)-和(+)-异洼地黄碱、(+)-洼地黄碱、(+)-洼地黄碱、(+)-和(±)-洼地黄碱、(+)-康定碱、(+)-石斛菪碱、(-)-斯库勒碱、卡普诺伊丁、去氢洼地黄碱、洼地黄胺、黄连碱；此外还有以下生物碱尚未作为该植物的组分描述：(+)-四氢洼地黄胺、异黄嘌呤、棕榈碱、小檗碱、去氢洼地黄酮、去氢洼地黄碱、(+)-α-石斛菪碱甲羟化物和生物碱CC2，以及新的中性生物碱去氢洼地黄胺、(+)-鼠曲草碱甲羟化物和α-四氢洼地黄胺甲羟化物。此外，还证明了洼地黄素、哥伦巴碱、黄连碱和芒黄素的存在。在空气部分中发现了(+)-鼠曲草碱、(+)-石斛菪碱、原品、卡普诺伊丁、黄漆碱、家禽生物碱CC1（可能是去氢家禽生物碱）、预中心碱、异博丁、洼地黄碱、黄连碱和微量的鼠曲草碱甲羟化物。
• Concise syntheses of 13-methylprotoberberine and 13-methyltetrahydroprotoberberine alkaloids
  作者：Wenchang Chen、Xiaofen Yi、Hongmin Qu、Yu Chen、Pei Tang、Fener Chen

  DOI：10.1016/j.cclet.2022.04.047

  日期：2022.12

  The concise syntheses of eight 13-methylprotoberberine (13-MePB) and eight enantioenriched 13-methyltetrahydroprotoberberine (13-MeTHPB) alkaloids have been achieved in a tactically modular fashion. This synthetic work features a one-pot metal-free Pictet-Spengler/Friedel-Crafts hydroxyalkylation/dehydration/oxidation sequence and a following highly enantioselective Ir-catalyzed hydrogenation. Given

  八种 13-甲基原小檗碱 (13-MePB) 和八种对映体富集的 13-甲基四氢原小檗碱 (13-MeTHPB) 生物碱的简明合成已以战术模块化方式实现。这项合成工作的特点是一锅法无金属 Pictet-Spengler/Friedel-Crafts 羟烷基化/脱水/氧化序列和随后的高度对映选择性 Ir 催化氢化。鉴于这种简洁性和模块化，我们开发的合成路线将非常有利于有效合成现有天然产物和 13-MePB 和 13-MeTHPB 家族的新全合成变体。