2-cyano-3-cyanomethyl-1-methyl-1,2,3,6-tetrahydropyridine | 143924-19-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2-cyano-3-cyanomethyl-1-methyl-1,2,3,6-tetrahydropyridine
• 英文别名: 2-Cyano-3-(cyanomethyl)-1,2,5,6-tetrahydropyridine；5-(cyanomethyl)-1-methyl-3,6-dihydro-2H-pyridine-6-carbonitrile
• CAS: 143924-19-0
• 化学式: C₉H₁₁N₃
• 分子量: 161.206
• InChiKey: HIFLPWQDQVPRID-UHFFFAOYSA-N

物化性质

• 沸点：
  326.8±42.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  50.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-cyano-3-cyanomethyl-1-methyl-1,2,3,6-tetrahydropyridine 在 盐酸 、 zinc chloride diethyl ether 、 三甲基铝 作用下， 以 四氢呋喃 为溶剂， 反应 25.0h， 生成
  参考文献：
  名称：

  “Tandem” reactivity of 2-Cyano-Δ3-piperideines II: Endocyclic versus exocyclic iminium ion reactions

  摘要：

  The C-7 substituted 2-cyano-DELTA-3-piperideine 2 reacts regioselectively with indole to give a 2/1 mixture of 4-(3-indolyl)piperidines 11 which were converted in four steps to the tetrahydropyridocarbazole derivative 16.

  DOI：

  10.1016/0040-4039(91)80131-o
• 作为产物：
  描述：

  3-吡啶乙腈 在 sodium tetrahydroborate 、 potassium carbonate 、 间氯过氧苯甲酸 、 三氟乙酸酐 、 柠檬酸 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 6.25h， 生成 2-cyano-3-cyanomethyl-1-methyl-1,2,3,6-tetrahydropyridine
  参考文献：
  名称：

  Synthesis of 20-deethylsilicine from a second-generation 2-cyano-.DELTA.3-piperidine synthon

  摘要：

  The Zn2+ ion mediated reaction of the 2-cyano-DELTA3-piperidine 9a (X = SO2C6H5) with the silyl enol ether of Na-methyl-2-acetylindole (24) led to formation of compounds 29a,b (70%) resulting from introduction of the acetylindole moiety at the exocyclic (C-7) carbon center and migration of the phenylsulfonyl group from C-7 to C-4. In contrast, reaction of 2-Cyano-DELTA3-piperidine 9b (X = CN) with 24 gave the desired C-4 acetylindole-substituted products 36a,b (1:1.3 mixture; 72% overall yield). Attempts to cyclize intermediates 36 to the tetracyclic enamine 27 were unsuccessful. Alternatively, the Zn2+-catalyzed reaction of synthons 9a and 9b with indole gave the C-7 indole-substituted aminonitriles 37a,b and 38, respectively. These intermediates were converted to DELTA2-piperidine 40 on reaction with sodium dimethyl malonate and AgBF4. Stereoselective hydrogenation of the enamine double bond in 40 furnished the required cis 3,4-disubstituted piperidine 41, which was cyclized under acidic conditions to the target molecule, 20-deethylsilicine (20).

  DOI：

  10.1021/jo00050a012

文献信息

• Synthetic applications of 2-(1,3-dithian-2-yl)indoles. IV. New synthesis of the tetracyclic ABED ring system of Strychnos alkaloids
  作者：Anna Diez、Josep Castells、Pilar Forns、Mario Rubiralta、David S. Grierson、Henri-Philippe Husson、Xavier Solans、Mercè Font-Bardía

  DOI：10.1016/s0040-4020(01)89689-7

  日期：——

  A new and versatile synthesis of tetracyclic compounds 10, 22 and 24 presenting the ABED ring system of Strychnos alkaloids is described by closure of the C1C11b bond in the key step. The intermediate tetrahydropyridinium salts 2 have been obtained from 2-(1,3-dithian-2-yl)indole (3) and either 2-cyano-3-ethyl-1-methyl-1,2,3,6-tetrahydropyridine (4a) or N-substituted Δ3-piperidein-2-ones (5).

  四环化合物的一种新的和通用的合成10，22和24呈现的ABED环系统马钱子生物碱是由C的闭合描述1 C 11B键在关键步骤。中间体四氢吡啶鎓盐2是从2-（1,3-二硫-2-基）吲哚（3）和2-氰基-3-乙基-1-甲基-1,2,3,6-四氢吡啶（图4a）或ñ -取代的Δ 3 -piperidein -2-酮（5）。
• Synthesis of 20-deethylsilicine from a second-generation 2-cyano-.DELTA.3-piperidine synthon
  作者：David S. Grierson、Jean Luc Bettiol、Ildiko Buck、Henri Philippe Husson、Mario Rubiralta、Anna Diez

  DOI：10.1021/jo00050a012

  日期：1992.11

  The Zn2+ ion mediated reaction of the 2-cyano-DELTA3-piperidine 9a (X = SO2C6H5) with the silyl enol ether of Na-methyl-2-acetylindole (24) led to formation of compounds 29a,b (70%) resulting from introduction of the acetylindole moiety at the exocyclic (C-7) carbon center and migration of the phenylsulfonyl group from C-7 to C-4. In contrast, reaction of 2-Cyano-DELTA3-piperidine 9b (X = CN) with 24 gave the desired C-4 acetylindole-substituted products 36a,b (1:1.3 mixture; 72% overall yield). Attempts to cyclize intermediates 36 to the tetracyclic enamine 27 were unsuccessful. Alternatively, the Zn2+-catalyzed reaction of synthons 9a and 9b with indole gave the C-7 indole-substituted aminonitriles 37a,b and 38, respectively. These intermediates were converted to DELTA2-piperidine 40 on reaction with sodium dimethyl malonate and AgBF4. Stereoselective hydrogenation of the enamine double bond in 40 furnished the required cis 3,4-disubstituted piperidine 41, which was cyclized under acidic conditions to the target molecule, 20-deethylsilicine (20).
• “Tandem” reactivity of 2-Cyano-Δ3-piperideines II: Endocyclic versus exocyclic iminium ion reactions
  作者：Jean-Luc Bettiol、Henri-Philippe Husson、David S. Grierson、Anna Diez、Mario Rubiralta

  DOI：10.1016/0040-4039(91)80131-o

  日期：1991.12

  The C-7 substituted 2-cyano-DELTA-3-piperideine 2 reacts regioselectively with indole to give a 2/1 mixture of 4-(3-indolyl)piperidines 11 which were converted in four steps to the tetrahydropyridocarbazole derivative 16.