N-(3-nitropyridin-2-yl)butylamine | 26820-68-8

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: N-(3-nitropyridin-2-yl)butylamine
• 英文别名: N-(3-nitro-2-pyridyl)butylamine；N-butyl-3-nitro-2-pyridinamine；2-butylamino-3-nitropyridine；N-butyl-3-nitropyridin-2-amine
• CAS: 26820-68-8
• 化学式: C₉H₁₃N₃O₂
• mdl: MFCD11118020
• 分子量: 195.221
• InChiKey: ZNWRAFXHMOAZLG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.444
• 拓扑面积：
  70.7
• 氢给体数：
  1
• 氢受体数：
  4

安全信息

• 海关编码：
  2933399090

反应信息

• 作为反应物：
  描述：

  溴甲苯 、 N-(3-nitropyridin-2-yl)butylamine 在 sodium hydride 作用下， 生成 1-Benzyloxy-2-propyl-1H-imidazo[4,5-b]pyridine
  参考文献：
  名称：

  Synthesis of N-alkoxybenzimidazoles and N-alkoxypyrimidazoles

  摘要：

  A variety of novel N-alkoxy aromatic-fused imidazoles have been prepared in a simple two-step process from 2-fluoro nitroaromatics and 2-chloro-3-nitropyridine. The imidazole forming step involves tandem heterocyclisation and O-alkylation with an in situ alkylating agent, and supports prior mechanistic proposals. Additional mechanistic experiments are described. The protocol is versatile with respect to both substrate halo-nitro aromatics and to the nature of the added electrophile (halides) used in the second step, and thereby significantly extends the scope of this reaction and its applicability to diverse synthesis. This methodology can also be used to generate various types of novel N-alkoxypyrimidazoles (4-deazapurine analogues), and an X-ray structure of one such pyrimidazole is presented. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)01841-5
• 作为产物：
  描述：

  2-羟基-3-硝基吡啶 以 乙腈 为溶剂， 反应 48.25h， 生成 N-(3-nitropyridin-2-yl)butylamine
  参考文献：
  名称：

  甲硅烷基化对硝基吡啶酮的实际胺化

  摘要：

  已开发出一种实用的方法，可通过用六甲基二硅氮烷处理将硝基吡啶酮（1）与伯胺偶联，从而避免使用有害试剂（如POCl 3）。吡啶基活化吡啶酮对于有效偶联是必要的，从而以良好的产率产生氨基硝基吡啶（3）。发现除3-硝基-4-吡啶酮（1）以外的区域异构体的反应性实质上较低，但会与伯胺偶联。

  DOI：

  10.1021/op800201u

文献信息

• Electrochemical Synthesis of Nitroanilines
  作者：Iluminada Gallardo、Gonzalo Guirado、Jordi Marquet

  DOI：10.1002/1099-0690(20021)2002:2<251::aid-ejoc251>3.0.co;2-a

  日期：2002.1

  Alkylamines and amides are readily prepared by nucleophilic aromatic substitution of hydrogen in nitroarenes by electrochemical oxidation. Useful yields (15−85%) are achieved in a simple direct and regioselective amination process. The synthetic method has been examined in the absence and presence of external bases, used to promote the first step of the nucleophilic aromatic substitution reaction, i.e

  烷基胺和酰胺很容易通过电化学氧化硝基芳烃中氢的亲核芳香取代来制备。有用的产率 (15-85%) 在简单的直接和区域选择性胺化过程中实现。该合成方法已在外部碱的存在和不存在下进行了检验，用于促进亲核芳族取代反应的第一步，即亲核攻击。在这两种情况下，都获得了良好的结果。在电化学氧化过程结束时，可以很容易地回收未反应的原料。这种新方法代表了一种对环境有利的氨基和酰胺取代硝基芳族化合物的途径。
• 1H and13C NMR studies of substituted nitropyridines and nitrobenzenes
  作者：N. S. Nudelman、S. B. Cerdeira

  DOI：10.1002/mrc.1260240607

  日期：1986.6

  observable with 2‐N‐butylamine‐, 2‐N‐cyclohexylamine‐ and 2‐(N‐piperidyl)‐substituted nitropyridines, whose 1H and 13C NMR spectra were also determined. In the case of the secondary amines, a hydrogen bond between the amino proton and the 3‐nitro group was clearly detected. 1H and 13C NMR spectra of 2,6‐dinitro‐, 2,4‐dinitro‐ and 2,4,6‐trinitro‐2‐R‐benzenes (R = OCH3, NHC4H9, NH‐cyclo‐C6H11, NC5H10) were

  已经测定了 3-硝基-、5-硝基-和 3,5-二硝基-2-甲氧基吡啶的 1H 和 13C NMR 谱。结果显示了 2-甲氧基优选的顺式构象，以及该基团的氧原子与阻碍 3-硝基取代衍生物共轭的邻硝基氧原子之间空间排斥的重要性。用 2-N-丁胺-、2-N-环己胺-和 2-(N-哌啶基)-取代的硝基吡啶也可以观察到类似的共振空间抑制，其 1H 和 13C NMR 光谱也被测定。在仲胺的情况下，可以清楚地检测到氨基质子和 3-硝基之间的氢键。2,6-二硝基-、2,4-二硝基-和2,4,6-三硝基-2-R-苯（R = OCH3、NHC4H9、NH-环-C6H11、NC5H10) 也被记录并与吡啶衍生物的那些进行比较。如果硝基的共轭不受阻碍，则电子氮杂和硝基效应是可比的。
• The Effects of Ring Substituents and Leaving Groups on the Kinetics of SNAr Reactions of 1-Halogeno- and 1-Phenoxy-nitrobenzenes with Aliphatic Amines in Acetonitrile
  作者：Michael R. Crampton、Thomas A. Emokpae、Chukwuemeka Isanbor

  DOI：10.1002/ejoc.200600968

  日期：2007.3

  attack although this may be mediated by reduced steric congestion around the reaction centre. Specific steric effects, leading to rate-retardation, is noted for the ortho-CF3 group. The 1-phenoxy compounds are subject to base catalysis and values of kAm/k–1 are reduced relative to more strongly activated compounds. This is likely to reflect increases in values of k–1 coupled with decreases in values of

  报告了一系列 1-氯-、1-氟-和 1-苯氧基-硝基苯的反应速率常数，这些苯由 CF3 或 CN 基团或环氮与正丁胺、吡咯烷或哌啶在乙腈中活化。将结果与先前报告的更强环活化化合物的结果进行比较。环活化的减少导致亲核攻击的 k1 值降低，尽管这可能是通过减少反应中心周围的空间拥挤来介导的。注意到邻位 组的特定空间效应导致速率延迟。1-苯氧基化合物受碱催化作用，相对于活性更强的化合物，kAm/k–1 值降低。这可能反映了 k-1 值的增加以及 kAm 值的降低，因为从两性离子中间体到催化胺的质子转移在热力学上变得不太有利。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Nucleophilic heteroaromatic substitution: Kinetics of the reactions of nitropyridines with aliphatic amines in dipolar aprotic solvents
  作者：Chukwuemeka Isanbor、Thomas A. Emokpae

  DOI：10.1002/kin.20297

  日期：2008.3

  reported for the reactions of 2-chloro-5-nitropyridine 2a, 2-chloro-3-nitropyridine 2b, and the corresponding 2-phenoxy derivatives 2c with n-butylamine, pyrrolidine and piperidine and 2d with n-butylamine and pyrrolidine in dimethyl sulfoxide (DMSO) as solvent. The same reactions in acetonitrile had been reported earlier (Crampton et al., Eur J Org Chem 2007, 1378–1383). Values in these solvents are compared

  报告了 2-氯-5-硝基吡啶 2a、2-氯-3-硝基吡啶 2b 和相应的 2-苯氧基衍生物 2c 与正丁胺、吡咯烷和哌啶以及 2d 与正丁胺和吡咯烷的反应速率数据以二甲亚砜 (DMSO) 为溶剂。早先已经报道了乙腈中的相同反应（Crampton 等人，Eur J Org Chem 2007，1378–1383）。这些溶剂中的值与 2,4-二硝基氯苯 3a、2,6-二硝基氯苯 3b 和相应的硝基活化二苯醚 3c 和 3d 的值进行比较。在两种溶剂中与正丁胺的反应给出了 kobs 值，该值随胺浓度线性增加，表明亲核攻击是速率限制的。唯一的例外是观察到碱催化的乙腈与 2c 的反应。k1 的值，亲核攻击的速率常数，按吡咯烷 > 哌啶 > 正丁胺的顺序递减。在乙腈中，动力学数据显示 k/k 比值大于 1，而在 DMSO 中则相反。对于苯氧基衍生物，取代是观察到的唯一过程。在 1-苯氧基衍生物的反应中
• The oxidative amination of 3-nitropyridines
  作者：Jan M Bakke、Harald Svensen

  DOI：10.1016/s0040-4039(01)00724-9

  日期：2001.6

  3-Nitropyridine was reacted with ammonia or alkylamines and KMnO4 under several different conditions. Substitutions in the pura posit ion to the nitro group were obtained with high regio selectivity: with ammonia, 2-amino-5-nitropyridine (66%), with butylamine, 2-butylamino-5-nitropyridine (92%), with diethylamine, 2-diethylamino-5-nitropyridine (49%). Under the same conditions, with methyl-3-nitroisonicotinoate and diethylamine/KMnO4, methyl 2-diethylamino-5-nitroisonicotinoate (48%), with 4-acetyl-3-nitropyridine (protected by ethylene glycol) 2-diethylamino-4-acetyl-5-nitropyridine (72%, protected) and with 4-cyano-3-nitropyridine, 2-amino-4-cyano-5-nitropyridine (41%) were obtained. All yields are isolated. (C) 2001 Elsevier Science Ltd. All rights reserved.