α-piperidino acrylonitrile | 74262-49-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: α-piperidino acrylonitrile
• 英文别名: α-Piperidinoacrylonitrile；2-(Piperidin-1-yl)propenenitrile；2-(1-piperidinyl)propenenitrile；2-piperidino acrylonitrile；1-piperidinoacrylonitrile；2-piperidinoacrylonitrile；2-Piperidin-1-ylprop-2-enenitrile
• CAS: 74262-49-0
• 化学式: C₈H₁₂N₂
• 分子量: 136.197
• InChiKey: HCQSTAGQTBLNCH-UHFFFAOYSA-N

物化性质

• 沸点：
  43-45 °C(Press: 5e-2 Torr)
• 密度：
  0.998±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  27
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  α-piperidino acrylonitrile 、 二叔丁基过氧化物 以 苯 为溶剂， 以64%的产率得到2,3-Bis[(2-methylpropan-2-yl)oxymethyl]-2,3-di(piperidin-1-yl)butanedinitrile
  参考文献：
  名称：

  Preparative trapping of tert-butoxy radicals by captodative olefins

  摘要：

  DOI：

  10.1016/s0040-4039(01)90013-9
• 作为产物：
  描述：

  3-Chloro-2-piperidin-1-yl-propionitrile 在 base 作用下， 生成 α-piperidino acrylonitrile
  参考文献：
  名称：

  Derdour, A.; Benabdallah, T.; Merah, B., Bulletin de la Societe Chimique de France, 1990, # 1, p. 69 - 78

  摘要：

  DOI：

文献信息

• One Step Regioselective Synthesis of 5-Aminoisoxazoles from Nitrile Oxides and α-Cyanoenamines
  作者：Amar Saad、Michel Vaultier、Aïcha Derdour

  DOI：10.3390/90700527

  日期：——

  The 1,3-dipolar cycloaddition of nitrile oxides to 1-cyanoenamines gives 5-aminoisoxazoles regioselectively. Moderate to good yields could be obtained depending on the method used to generate the nitrile oxides. The intermediate isoxazolines could not be isolated.

  腈氧化物与1-氰基烯胺的1,3-偶极环加成反应区域选择性地合成了5-氨基异恶唑。根据产生腈氧化物的方法不同，产率从中等到良好不等。中间体异恶唑啉无法被分离出来。
• Light induced reactions of substituted 1-acetonaphthones with 2-piperidinopropenenitrile. Part IIIFor part II, see ref. 17.
  作者：Memarian、Nasr-Esfahani、Doepp

  DOI：10.1039/b105445g

  日期：2001.12.3

  UV excitation (λ≥280 nm) of 1-acetonaphthones additionally substituted at C-2 or C-4 in the presence of 2-piperidinopropenenitrile resulted in the occurrence of two types of reactions, photocycloaddition and photosubstitution. Whereas photosubstitution has occurred only in the case of halogen substituents, the formation of [4+2]- and [2+2]-cycloadducts has been observed, which is dependent on the location

  UV激发（λ ≥ 1- acetonaphthones在C-2或C-4中的存在附加地取代的280纳米）2-哌啶子基丙烯腈导致发生两种类型的反应：光环加成和光解。尽管仅在卤素取代基的情况下才发生光解，但已观察到[4 + 2]-和[2 + 2]-环加合物的形成，这取决于环上其他取代基的位置。
• α-Cyclization of tertiary amines. Part 3. Captodative or push-pull enamines form pyrrolines, pyrrolizidines and their ring homologues with dimethyl acetylenedicarboxylate in a highly diastereoselective reaction
  作者：Benoît De Boeck、Shuiping Jiang、Zdenek Janousek、Heinz G. Viehe

  DOI：10.1016/s0040-4020(01)85235-2

  日期：1994.1

  The title one-pot reaction occurs through a sequence of [2+2] cycloaddition, ring opening to dienamines and formation of a 1,5-dipole by [1,6] hydrogen-shift. This intermediate may cyclize or, in sterically suitable cases and at lower temperatures, lead to isolable N-vinyl enamines by proton transfer.

  通过[2 + 2]环加成，二烯胺开环和通过[1,6]氢转移形成1,5-偶极的过程发生标题一锅反应。该中间体可环化，或在空间上合适的情况下且在较低温度下通过质子转移产生可分离的N-乙烯基烯胺。
• [2 + 2] Photoaddition of 2-aminopropenenitriles to diarylethanediones. A product study
  作者：Dietrich Döpp、Michael-Alexander Fischer

  DOI：10.1002/recl.19951141114

  日期：——

  and unsymmetrical (4a,b) diarylethanediones, starting from their 3(n, π*) states, undergoes smooth head-to-head [2 + 2] photoaddition of various 2-aminopropenenitriles 2A-F to form oxetanes 3, 5 and 6 in moderate to good yields. Only one diastereomer out of two a-priori possible regioisomers is formed in each case. The connectivity and the preferred geometry of the products is rationalized in terms

  从它们的3（n，π*）状态开始，选择对称的（1a-f）和不对称的（4a，b）二芳基乙二酮，对各种2-氨基丙烯腈2A-进行平滑的头对头[2 + 2]光加成。F以中等至良好的产率形成氧杂环丁烷3、5和6。在每种情况下，在两种先验可能的区域异构体中仅形成一种非对映异构体。产品的连通性和首选几何形状是根据最容易获得和最稳定的（包括俘获稳定性）1,4-双自由基中间体的几何形状进行合理化的。而2-萘基取代的二酮1f和4b 氧杂环丁烷，1,1'-萘和1-（1-萘基）-2-苯基乙二酮无效。
• Oxetanes from Photocycloaddition of 2-Aminopropenenitriles to Methyl Phenylglyoxylate and Benzils
  作者：Christiane van Wolven、Dietrich Döpp、Gerald Henkel

  DOI：10.1515/znb-2006-0310

  日期：2006.3.1

  By irradiation of methyl phenylglyoxylate (1) in benzene solution in presence of equimolar amounts of 2-aminopropenenitriles H₂C=C(NR₂)CN (3a - e, NR2 = morpholino, 1-pyrrolidinyl, 1-piperidinyl, hexamethyleneimino, heptamethyleneimino) the corresponding 2R^∗,3R^∗ head-to-head oxetanes 4a - e were obtained in moderate yields (11 - 52%) along with 2 - 28% of rac-dimethyl 2,3- diphenyltartrate (2). In presence of (S)-2-(2-methoxymethylpiperidin-1-yl)propenenitrile ((+)-3g) 1 is transformed into 26% of 2 and 33% of a mixture of diastereomeric oxetanes 4g,4’g in a ratio of 1.4 : 1 which could be improved to 2.5 : 1 by preparative layer chromatography. The absolute configuration of the major diastereomer 4g was unambiguously confirmed by a single crystal X-ray structure determination to be 2R,3R,2’S. Analogous photoadditions to benzil (5a), 4,4’-bis-(trifluoromethyl)benzil (5b) and 4,4’-dichlorobenzil (5c) with (+)-3g and its lower homologue (S)-2-(2-methoxymethylpyrrolidin- 1-yl)propenenitrile ((-)-3f) gave oxetanes only in low yield as detected by ¹H NMR. Byproducts arise from competitive symmetrical α-cleavage of 5.

  在苯溶液中照射甲基苯基乙酰乳酸酯（1），在存在等摩尔量的2-氨基丙烯腈H₂C=C(NR₂)CN（3a - e，NR2 =吗啡啶基，1-吡咯啉基，1-哌啶基，己亚甲基亚胺基，庚亚甲基亚胺基）的情况下，得到相应的2R^∗,3R^∗头对头噁嗪醇（oxetanes）4a - e，产率中等（11 - 52%），同时还有2 - 28%的消旋二甲基2,3-二苯基酒石酸酯（2）。在（S）-2-（2-甲氧基甲基哌啶-1-基）丙烯腈（（+）-3g）存在下，1转化为26%的2和33%的2个不对映异构体噁嗪醇4g,4’g的混合物，比例为1.4：1，经制备层析层析法可提高至2.5：1。主要对映异构体4g的绝对构型通过单晶X射线结构测定明确为2R,3R,2’S。与（+）-3g及其较低同系物（S）-2-（2-甲氧基甲基吡咯啉-1-基）丙烯腈（（-）-3f）对苯并二酮（5a）、4,4’-双（三氟甲基）苯并二酮（5b）和4,4’-二氯苯并二酮（5c）的类似光加成反应仅以低收率生成噁嗪醇，通过¹H NMR检测，副产物来自对5的竞争性对称α-裂解。