Tropidin | 529-18-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: Tropidin
• 英文别名: 2-Tropene；(1R,5S)-8-methyl-8-azabicyclo[3.2.1]oct-2-ene
• CAS: 529-18-0；122709-67-5
• 化学式: C₈H₁₃N
• 分子量: 123.198
• InChiKey: RNHFKJBXKFGPIY-JGVFFNPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2933990090
• 危险性防范说明：
  P280,P305+P351+P338
• 危险性描述：
  H317,H319
• 储存条件：
  | 温度范围：2-8°C |

反应信息

• 作为反应物：
  描述：

  Tropidin 在 4-二甲氨基吡啶 、 sodium hydroxide 、 1-氯乙基氯甲酸酯 、 双氧水 、 sodium cyanoborohydride 、 sodium carbonate 、 三乙胺 、 三氟乙酸 、 sodium nitrite 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 、 乙酸酐 、 溶剂黄146 、 乙腈 为溶剂， 反应 127.17h， 生成 古卡因
  参考文献：
  名称：

  Enantiospecific Synthesis of Natural (−)-Cocaine and Unnatural (+)-Cocaine from d- and l-Glutamic Acid

  摘要：

  Natural (-)-cocaine and unnatural (+)-cocaine have been synthesized enantiospecifically from D- and L-glutamic acid, respectively. The axial-equatorial substitutents were introduced by a stereo- and regiospecific dipolar cycloaddition to the corresponding (LR,5S)- and (1S,5R)-N-BOC-nortropenes with (ethoxycarbonyl)formonitrile N-oxide. A sequence of subsequent stereochemically controlled transformations converted the fused isoxazoline to the requisite P-hydroxy ester. Synthesis of the key intermediate N-BOC-nortropenes involved construction of the 8-azabicyclo[3.2.1]octane framework by Dieckmann condensation of cis-5-substituted D-and L-proline esters. For comparison, (1R,SS)-N-BOC-nortropene also was derived by degradation from natural cocaine. The cis-5-substituted D-and L-proline esters were obtained by sulfide contraction and subsequent catalytic hydrogenation to induce stereospecifically the C-5 stereochemistry from D-and L-thiopyroglutamate, which in turn were prepared from D-and L-glutamic acids, respectively.

  DOI：

  10.1021/jo980153t
• 作为产物：
  描述：

  盐酸古柯碱 在 palladium on activated charcoal 盐酸 、 1-氧化-2-巯基吡啶 、 sodium periodate 、 草酰氯 、 氢气 、 N,N-二甲基甲酰胺 作用下， 以 甲醇 、 水 为溶剂， 75.0 ℃ 、413.69 kPa 条件下， 反应 48.0h， 生成 Tropidin
  参考文献：
  名称：

  Enantiospecific Synthesis of Natural (−)-Cocaine and Unnatural (+)-Cocaine from d- and l-Glutamic Acid

  摘要：

  Natural (-)-cocaine and unnatural (+)-cocaine have been synthesized enantiospecifically from D- and L-glutamic acid, respectively. The axial-equatorial substitutents were introduced by a stereo- and regiospecific dipolar cycloaddition to the corresponding (LR,5S)- and (1S,5R)-N-BOC-nortropenes with (ethoxycarbonyl)formonitrile N-oxide. A sequence of subsequent stereochemically controlled transformations converted the fused isoxazoline to the requisite P-hydroxy ester. Synthesis of the key intermediate N-BOC-nortropenes involved construction of the 8-azabicyclo[3.2.1]octane framework by Dieckmann condensation of cis-5-substituted D-and L-proline esters. For comparison, (1R,SS)-N-BOC-nortropene also was derived by degradation from natural cocaine. The cis-5-substituted D-and L-proline esters were obtained by sulfide contraction and subsequent catalytic hydrogenation to induce stereospecifically the C-5 stereochemistry from D-and L-thiopyroglutamate, which in turn were prepared from D-and L-glutamic acids, respectively.

  DOI：

  10.1021/jo980153t

文献信息

• Die sterischen Bedingungen der Fragmentierungsreaktion I. Teil. Stereoisomere 3-Chlortropane. Fragmentierungsreaktionen, 14. Mitteilung
  作者：A. T. Bottini、C. A. Grob、E. Schumacher、J. Zergenyi

  DOI：10.1002/hlca.19660490815

  日期：——

  The steric requirements for the synchronous fragmentation of γ-aminohalides as previously postulated have been confirmed by a study of the solvolysis of stereoisomeric 3β- and 3β-chloro-tropanes and -nortropanes. 3β-chloro-tropanes (7 a) and 3β-chloro-nortropane (7 b), which fulfil the stereoelectronic requirements, undergo quantitative fragmentation in 80 vol.% ethanol. They react 1.35 × 104 and 1

  通过对立体异构体3β-和3β-氯代-托环烷和-降冰片烷的溶剂分解研究，证实了先前假设的γ-氨基卤化物同步断裂的空间要求。满足立体电子要求的3β-氯-托烷（7a）和3β-氯-烷托烷（7b）在80％（体积）的乙醇中进行定量裂解。它们的反应速度分别为1.35×10 4和1.35×10 3倍，与“同质” exo -3-氯-双环[3.2.1]辛烷（12 a）一样快。因此，碎片是通过同步机制发生的。
• Cationic Tropidinyl Scandium Catalyst: A Perfectly Acceptable Substitute for Cationic Half-Sandwich Scandium Catalysts in <i>cis</i>-1,4-Polymerization of Isoprene and Copolymerization with Norbornene
  作者：Siqian Liu、Gaixia Du、Jianyun He、Yingyun Long、Shaowen Zhang、Xiaofang Li

  DOI：10.1021/ma500740m

  日期：2014.6.10

  tris(trimethylsilylmethyl) rare earth metal complexes with the readily available natural product tropidine. The polymerization experiments indicate that the monotropidinyl scandium dialkyl complex 1 displays reactivity akin to that of the analogous monocyclopentadienyl scandium dialkyl complexes. In the presence of activator and a small amount of AlMe3, complex 1 exhibits similar activities (up to 1.6

  不同的非金属茂稀土金属烷基络合物，例如单tropidinyl（Trop）di二烷基络合物（Trop）Sc（CH 2 SiMe 3）2（THF）（1），ditropidinyl钇烷基络合物（Trop）2 Y（CH 2 SiMe 3）（ THF）（3）以及带有一个四齿双阴离子6 - N-甲基-1,4-环庚二烯基（NMCH）配体[（NMCH）Lu（CH 2 SiMe 3）（THF）]的双核烷基络合物2（2）已通过一锅酸碱反应，通过使用三（三甲基甲硅烷基甲基）稀土金属配合物与现成的天然产品托帕定进行了高收率的合成。聚合实验表明，单斜环炔基scan二烷基络合物1显示出与类似的单环戊二烯基scan二烷基络合物相似的反应性。在存在活化剂和少量AlMe 3的情况下，配合物1表现出相似的活性（高达1.6×10 6 g mol Sc –1 h –1），但比cis -1,4-选择性（高达100％）高（C 5 H
• Efficient Direct Synthesis of Tropidinyl Titanium and Zirconium Complexes by Allylic CH-Activation of 8-Methyl-8-azabicyclo[3.2.1]oct-2-ene (Tropidine)
  作者：Matthias Tamm、Andreas Kunst、Michael Stadler、Eberhardt Herdtweck

  DOI：10.1021/om0609564

  日期：2007.1.1

  A CH-activation and deprotonation of 8-methyl-8-azabicyclo[3.2.1]oct-2-ene (tropidine, 1) occurs upon reaction with TiCl4 and ZrCl4 to afford the allyl complexes monotropidinyl titanium trichloride (4) and ditropidinyl zirconium dichloride (7), respectively. Tropidine (1) itself acts as the HCl scavenger, and the reactions are accompanied by the formation of 1 equiv of the hydrochloride 1·HCl. The

  与TiCl 4和ZrCl 4反应得到8-甲基-8-氮杂双环[3.2.1]辛-2-烯（托丁啶，1）的CH活化和去质子化，得到烯丙基络合物单氯化物三氯化钛（4）和二氯化噻吩啶基锆（7）。Tropidine（1）本身是HCl的清除剂，反应伴随形成1当量的盐酸盐1 ·HCl。报告了4的晶体结构。
• Ladenburg, Chemische Berichte, 1879, vol. 12, p. 944
  作者：Ladenburg

  DOI：——

  日期：——
• Merling, Chemische Berichte, 1892, vol. 25, p. 3124
  作者：Merling

  DOI：——

  日期：——