2-(cyanomethyl)-1-(4-methylbenzyl)aziridine | 897440-36-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(cyanomethyl)-1-(4-methylbenzyl)aziridine
• 英文别名: 2-[1-[(4-Methylphenyl)methyl]aziridin-2-yl]acetonitrile
• CAS: 897440-36-7
• 化学式: C₁₂H₁₄N₂
• 分子量: 186.257
• InChiKey: QNEQWPLNBBAEHX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  26.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(cyanomethyl)-1-(4-methylbenzyl)aziridine 在 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 3.0h， 生成 (2Z)-4-[N-(4-methylbenzyl)-N-benzylamino]-2-butenenitrile
  参考文献：
  名称：

  Novel Synthesis of 3,4-Diaminobutanenitriles and 4-Amino-2-butenenitriles from 2-(Cyanomethyl)aziridines through Intermediate Aziridinium Salts:  An Experimental and Theoretical Approach

  摘要：

  1-Arylmethyl-2-(cyanomethyl)aziridines were transformed into 4-(N,N-bis(arylmethyl)amino)-3-(pyrrolidin-1-yl)butanenitriles and 4-(N,N-bis(arylmethyl)amino)-2-butenenitriles via 4-(N,N-bis(arylmethyl)amino)-3-bromobutanenitriles in high yields and purity. The key steps involve the unprecedented regiospecific ring opening of intermediate 2-(cyanomethyl)aziridinium salts by bromide and pyrrolidine in acetonitrile, exclusively at the substituted aziridine carbon atom. The results were rationalized on the basis of ab initio calculations.

  DOI：

  10.1021/jo0704210
• 作为产物：
  描述：

  potassium cyanide 、 2-(溴甲基)-1-[(4-甲基苯基)甲基]氮杂环丙烷 以 二甲基亚砜 为溶剂， 以70%的产率得到2-(cyanomethyl)-1-(4-methylbenzyl)aziridine
  参考文献：
  名称：

  Synthesis of 2-[(Arylmethylene)amino]cyclopropanecarbonitriles via a Two-Step Ring Transformation of 2-(Cyanomethyl)aziridines

  摘要：

  2-(氰基甲基)氮杂环丁烯与N-溴琥珀酰亚胺在二氯甲烷中的反应生成高收率的3-[(芳烯基)氨基]-4-溴丁腈。后者的β-氨基-γ-溴丁腈通过与醋酸钾的反应进行1,3-环化，转化为可分离的反式和顺式2-[(芳烯基)氨基]环丙烷碳腈，从而完成了2-(氰基甲基)氮杂环丁烯到2-[(芳烯基)氨基]环丙烷碳腈的两步环转化。

  DOI：

  10.1055/s-0028-1088000

文献信息

• Synthesis of 1-Arylmethyl-2-(cyanomethyl)aziridines and Their Ring Transformation into Methyl <i>N</i>-(2-Cyanocyclopropyl)benzimidates
  作者：Matthias D'hooghe、Sven Mangelinckx、Evelien Persyn、Willem Van Brabandt、Norbert De Kimpe

  DOI：10.1021/jo060425p

  日期：2006.5.1

  α-dichlorobenzyl)amino)butanenitriles with sodium methoxide in methanol resulted in novel methyl N-(2-chloro-1-(cyanomethyl)ethyl)benzimidates, although in low yields. The latter γ-chloro nitriles were smoothly converted into methyl N-(2-cyanocyclopropyl)benzimidates as precursors of biologically relevant β-ACC derivatives through a 1,3-cyclization protocol by reaction with potassium tert-butoxide in THF

  在DMSO中用氰化钾处理后，可以由相应的2-（溴甲基）氮丙啶高产率地制备1-芳基甲基-2-（氰基甲基）氮丙啶。在CCl 4中用N-氯琥珀酰亚胺将氮丙啶部分开环，然后在甲醇中用甲醇钠处理由此形成的4-氯-3-（N-氯-N-（α，α-二氯苄基）氨基）丁腈。新颖甲基ñ - （2-氯-1-（氰基甲基）乙基）benzimidates，虽然在低的产率。后者的γ-氯腈通过与钾反应的1,3-环化方案被平滑地转化为N-（2-氰基环丙基）苯并亚甲基丙烯酸酯作为生物相关的β-ACC衍生物的前体在THF中的叔丁醇盐。
• Opposite Regiospecific Ring Opening of 2-(Cyanomethyl)aziridines by Hydrogen Bromide and Benzyl Bromide: Experimental Study and Theoretical Rationalization
  作者：Saron Catak、Matthias D’hooghe、Toon Verstraelen、Karen Hemelsoet、Andries Van Nieuwenhove、Hyun-Joon Ha、Michel Waroquier、Norbert De Kimpe、Veronique Van Speybroeck

  DOI：10.1021/jo100687q

  日期：2010.7.2

  Ring opening of 1-arylmethyl-2-(cyanomethyl)aziridines with HBr afforded 3-(arylmethyl)amino-4-bromobutyronitriles via regiospecific ring opening at the unsubstituted aziridine carbon. Previous experimental and theoretical reports show treatment of the same compounds with benzyl bromide to furnish 4-amino-3-bromobutanenitriles through ring opening at the substituted aziridine carbon. To gain insights

  1-芳基甲基-2-（氰基甲基）氮丙啶与HBr的开环通过在未取代的氮丙啶碳上的区域特异性开环而提供3-（芳基甲基）氨基-4-溴丁腈。以前的实验和理论报告表明，用苄基溴处理相同的化合物，可通过在取代的氮丙啶碳上开环提供4-氨基-3-溴丁腈。为了深入了解HBr的区域选择性偏好，已使用计算方法分析了反应路径。通过使用显式溶剂分子考虑了溶剂化的影响。几何形状是在B3LYP / 6-31 ++ G（d，p）的理论水平上确定的，其中包括Grimme型校正项，用于长距离色散相互作用。亚杂化MPW1B95的功能改善了相对能量。活化屏障证实了对于HBr而言，在未取代的环碳上优选开环。通过比较相应的叠氮鎓中间体的电子结构，分析了HBr与苄基溴的开环。尽管静电图像无法解释反应的相反区域特异性，但LUMO和亲核Fukui函数的前沿分子轨道分析显示出对苄基溴情况下的取代氮丙啶碳和HBr中未取代的氮丙啶碳明显的攻击偏好
• Ring opening of 2-(cyanomethyl)aziridines by acid chlorides: synthesis of novel 4-amino-2-butenenitrile derivatives through intermediate aziridinium salts
  作者：Matthias D’hooghe、Karel Vervisch、Andries Van Nieuwenhove、Norbert De Kimpe

  DOI：10.1016/j.tetlet.2007.01.039

  日期：2007.3

  1-Arylmethyl-2-(cyanomethyl)aziridines were transformed into novel N-arylmethyl-N-(2-chloro-3-cyanopropyl)amides as the major reaction products upon treatment with acid chlorides in CH2Cl2 through the ring opening of intermediate aziridinium salts. Subsequently, N-arylmethyl-N-(2-chloro-3-cyanopropyl)amides were converted into stable N-arylmethyl-N-(3-cyano-2-propenyl)amides for the first time by means

  通过在CH 2 Cl 2中通过酰基氯的开环处理，将1-芳基甲基-2-（氰基甲基）氮丙啶转化为新颖的N-芳基甲基-N-（2-氯-3-氰基丙基）酰胺作为主要反应产物。中间体叠氮鎓盐。随后，Ñ -arylmethyl- ñ - （2-氯- 3-氰基丙基）酰胺转化成稳定Ñ -arylmethyl- Ñ通过介导的Et脱氯化氢的方法（3-氰基-2-丙烯基）酰胺首次- 3 N的CH 2氯2。
• Novel synthesis of 2-aminopentanedinitriles from 2-(bromomethyl)aziridines and their transformation into 2-imino-5-methoxypyrrolidines and 5-methoxypyrrolidin-2-ones
  作者：Matthias D'hooghe、Andries Van Nieuwenhove、Willem Van Brabandt、Mario Rottiers、Norbert De Kimpe

  DOI：10.1016/j.tet.2007.03.116

  日期：2008.2

  1-Arylmethyl-2-(bromomethyl)aziridines were transformed into 2-[N-(arylmethyl)amino]pentanedinitriles upon treatment with an excess of potassium cyanide in DMSO through an unprecedented and peculiar reaction mechanism, involving base-induced ring opening of intermediate 2-(cyanomethyl)aziridines into allylamines, followed by migration of the double bond out of the conjugation towards aldimines via enamine intermediates. The resulting aminopentanedinitriles, served as substrates for the synthesis of novel 2-imino-5-methoxypyrrolidines upon treatment with sodium methoxide in methanol, which were either acetylated at the free imino group to afford the more stable N-acetylimino derivatives or hydrolyzed towards the corresponding synthetically relevant 5-methoxypyrrolidin-2-ones. (c) 2007 Elsevier Ltd. All rights reserved.
• Synthesis of 2-[(Arylmethylene)amino]cyclopropanecarbonitriles via a Two-Step Ring Transformation of 2-(Cyanomethyl)aziridines
  作者：Norbert De Kimpe、Sven Mangelinckx、Matthias D’hooghe、Sietske Peeters

  DOI：10.1055/s-0028-1088000

  日期：2009.4

  Reaction of 2-(cyanomethyl)aziridines with N-bromosuccinimide in dichloromethane results in the formation of 3-[(arylmethylene)amino]-4-bromobutanenitriles in high yield. The latter β-amino-γ-bromobutanenitriles were converted into separable trans- and cis-2-[(arylmethylene)amino]cyclopropanecarbonitriles through a 1,3-cyclization by reaction with potassium tert-butoxide, thus culminating in a two-step ring transformation of 2-(cyano­methyl)aziridines into 2-[(arylmethylene)amino]cyclopropanecarbonitriles.

  2-(氰基甲基)氮杂环丁烯与N-溴琥珀酰亚胺在二氯甲烷中的反应生成高收率的3-[(芳烯基)氨基]-4-溴丁腈。后者的β-氨基-γ-溴丁腈通过与醋酸钾的反应进行1,3-环化，转化为可分离的反式和顺式2-[(芳烯基)氨基]环丙烷碳腈，从而完成了2-(氰基甲基)氮杂环丁烯到2-[(芳烯基)氨基]环丙烷碳腈的两步环转化。