1,4,5,6-四氢-3-吡啶甲腈 | 7492-87-7

• 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
• 中文名称: 1,4,5,6-四氢-3-吡啶甲腈
• 英文名称: 1,4,5,6-tetrahydropyridine-3-carbonitrile
• 英文别名: 1,4,5,6-Tetrahydro-3-pyridinecarbonitrile；1,2,3,4-tetrahydropyridine-5-carbonitrile
• CAS: 7492-87-7
• 化学式: C₆H₈N₂
• mdl: MFCD09701419
• 分子量: 108.143
• InChiKey: UWFYMNQYYJQPRQ-UHFFFAOYSA-N

物化性质

• 熔点：
  38-39 °C
• 沸点：
  145 °C
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  35.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4,5,6-四氢-3-吡啶甲腈 在 sodium periodate 、 正丁基锂 、 氧气 、 potassium hydride 作用下， 以 甲醇 为溶剂， 反应 10.0h， 生成 (+/-)-(1'S,3'R,9S,9aR)-1,3,4,6,7,8,9,9a-octahydro-2H-quinolizine-1-spiro-2'-(1',3'-dioxo-1',3'-dithiane)-9-carbonitrile
  参考文献：
  名称：

  α,β-Unsaturated Nitriles:  Stereoselective Conjugate Addition Reactions

  摘要：

  Dithiane anions undergo intramolecular conjugate additions with alpha,beta-unsaturated nitriles when a dithiane anion is tethered to N-1 of the 3-cyano-1,4,5,6-tetrahydropyridine nucleus. 3-Cyano-1-[2-(1,3-dithianyl-2-yl)ethyl]-1,4,5,6-tetrahydropyridine (1a) and the one-carbon homologue 1b cyclize in the presence of 12-crown-4 to generate indolizidine 3 and quinolizidine 9, in which the nitrile group exhibits a strong, thermodynamic preference for the axial orientation. Oxidation of Ib provides dithiane S-oxide 10 that undergoes a highly stereoselective conjugate addition to provide crystalline quinolizidine 13. The X-ray structure of 13 is reported and corroborates our ''peg-in-a-pocket'' principle for stereoselective conjugate additions with alpha,beta-unsaturated nitriles.

  DOI：

  10.1021/jo9619894
• 作为产物：
  描述：

  3-氰基吡啶 在 2-[7-(2-Diphenylphosphanylethyl)-1,5-diphenyl-1,5,3,7-diazadiphosphocan-3-yl]ethyl-diphenylphosphane 、 potassium tert-butylate 、 氢气 、 cobalt(II) bromide 作用下， 以 异丙醇 为溶剂， 80.0 ℃ 、500.01 kPa 条件下， 以58 %的产率得到1,4,5,6-四氢-3-吡啶甲腈
  参考文献：
  名称：

  Co/P4N2 催化剂的均相脱芳烃加氢：一种亲核方法

  摘要：

  已被证明是强氢化物供体的Co(P 4 N 2 )H 物种可以以亲核方式将氢阴离子传递给电子富集程度较低的芳烃和杂芳烃。氘标记实验支持迈克尔型反应途径。已进行理论分析以研究 CoH 物种的水合性和芳烃的亲电子性。

  DOI：

  10.1002/chem.202203189

文献信息

• Homogeneous Hydrogenation with a Cobalt/Tetraphosphine Catalyst: A Superior Hydride Donor for Polar Double Bonds and <i>N</i>-Heteroarenes
  作者：Ya-Nan Duan、Xiaoyong Du、Zhikai Cui、Yiqun Zeng、Yufeng Liu、Tilong Yang、Jialin Wen、Xumu Zhang

  DOI：10.1021/jacs.9b11070

  日期：2019.12.26

  The development of catalysts based on earth abundant metals in place of noble metals is becoming a central topic of catalysis. We herein report a cobalt/tetraphosphine complex catalyzed homogeneous hydrogenation of polar unsaturated compounds using an air- and moisture-stable and scalable precatalyst. By activation with potassium hydroxide, this cobalt system shows both high efficiency (up to 24000

  基于地球上丰富的金属代替贵金属的催化剂的开发正在成为催化的中心话题。我们在此报告了一种钴/四膦配合物催化的极性不饱和化合物的均相氢化反应，该反应使用空气和水分稳定且可缩放的预催化剂。通过用氢氧化钾活化，该钴系统显示出高效率（高达 24000 TON 和 12000 h-1 TOF）和对各种醛、酮、亚胺甚至 N-杂芳烃的优异化学选择性。1,2-还原优于 1,4-还原使该方法成为制备烯丙醇和胺的有效方法。同时，具有挑战性的 N-杂芳烃的有效氢化也具有优异的官能团耐受性。机理研究和控制实验表明 CoIH 复合物在催化循环中起到强氢化物供体的作用。对催化循环中的每个钴中间体进行了表征，并提出了一种合理的外球机制。值得注意的是，外部无机碱在该反应中起着多种作用，并且几乎在催化循环的每一步都起作用。
• New Synthetic Approach to 4-(3-Aminopropyl)-5-amino-1-methylpyrazole Starting from 3-Cyanopyridine
  作者：Atsushi Ohigashi、Kiyoshi Temmaru、Norio Hashimoto

  DOI：10.1021/op0501996

  日期：2006.1.1

  regioselective enamine exchange with N-methylhydrazine and 1,4,5,6-tetrahydro-pyridine-3-carbonitrile (8), followed by a subsequently occurring intramolecular cyclization and aromatization, starting from a cheap 3-cyanopyridine (7).

  为4-（合成短，实用的方法Ñ -Boc-3-氨基丙基）-5-（Ñ -tritylamino）-1-甲基吡唑（3），抗侧链绿脓杆菌头孢菌素FR259647，1，是通过利用与N-甲基肼和1,4,5,6-四氢吡啶-3-甲腈的区域选择性烯胺交换（8）建立，随后进行随后的分子内环化和芳构化，从廉价的3-氰基吡啶（7）。
• [4 + 2]-Cycloaddition Reactions between β-Acceptor-Substituted Enamines and 2-Vinylindole Radical Cations Acting as Hetero-Dienes
  作者：Christoph F. Gürtler、Eberhard Steckhan、Siegfried Blechert

  DOI：10.1021/jo951551o

  日期：1996.1.1

  [4 + 2]-Cycloaddition reactions between 2-vinylindoles acting as hetero-dienes and beta-acceptor substituted cyclic and acyclic enamines can be induced by formation of 2-vinylindole radical cations either via anodic oxidation or photoelectron transfer (PET) using catalytic amounts of triarylpyrylium tetrafluoroborates as sensitizers. In this way, pyrido[1,2-a]indoles or indolo[1,2-a]hexahydro-1,8-naphthyridines

  充当杂二烯的2-乙烯基吲哚与β-受体取代的环状和无环烯胺之间的[4 + 2]-环加成反应可以通过使用催化量的阳极氧化或光电子转移（PET）形成2-乙烯基吲哚自由基阳离子来诱导四氟硼酸三芳基吡啶鎓作为敏化剂。以此方式，在完整的区域和立体化学控制下，一步形成吡啶并[1,2-a]吲哚或吲哚[1,2-a]六氢-1,8-萘啶。
• Reactivity of 2-cyano-1,4,5,6-tetrahydro-1-pyridinecarboxylic acid esters towards various nucleophiles: Regio- and stereoselectivity of the attack
  作者：P. Stanetty、M. D. Mihovilovic、K. Mereiter

  DOI：10.1007/bf00806971

  日期：1997.10

  The synthesis and reactivity of the title compounds towards nucleophiles are discussed. The regio-and diastereoselectivity of the attack is highly dependent on the carbamic ester and the type of nucleophile applied. Both Michael type addition across the activated double bond and S(N)2T reaction at the carbamate carbon atom were observed. Structure assignment of the adducts in solution and in the solid state was performed utilizing high temperature NMR techniques as well as single crystal X-ray diffraction.
• 3-Cyano-1-[4-(1,3-dithian-2-yl)butyl]-1,4,5,6-tetrahydropyridine
  作者：Z. Hussain、F. F. Fleming、R. E. Norman、S. C. Chang

  DOI：10.1107/s010827019501345x

  日期：1996.4.15

  The title nitrile 1-[4-(1,3-dithian-2-yl)butyl]-1,4,5,6-tetrahydropyridine-3-carbonitrile, C14H22N2S2} was prepared as part of our investigations into the conjugate addition reactions of unsaturated nitriles [Fleming & Pak (1995). J. Org. Chem. 60, 4299-4301]. The tetrahydropyridine ring adopts a half-chair conformation and is appended by a four-carbon chain to the dithiane ring which adopts a chair conformation.