N-benzyl-N-nitrosopivalamide | 100253-83-6

• 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: N-benzyl-N-nitrosopivalamide
• 英文别名: Propanamide, 2,2-dimethyl-N-nitroso-N-(phenylmethyl)-；N-benzyl-2,2-dimethyl-N-nitrosopropanamide
• CAS: 100253-83-6
• 化学式: C₁₂H₁₆N₂O₂
• 分子量: 220.271
• InChiKey: AKNHXSGWJZXTJG-UHFFFAOYSA-N

物化性质

• 沸点：
  311.5±35.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  49.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-benzyl-N-nitrosopivalamide 以 various solvent(s) 为溶剂， 反应 1.0h， 以100%的产率得到2,2-二甲基丙酸苯甲酯
  参考文献：
  名称：

  Darbeau–White–Gibble反应：N-亚硝基酰胺介导的Ritter型反应。第一部分：亲核试剂中电子，空间和轨道效应的研究

  摘要：

  苄基 阳离子是通过生成的 热分解 的 N-苄基-N-亚硝基新戊酰胺在熔融的4-R-取代的苄腈中（R ＝ NH 2，Me 2 N，MeO，Me，H，F和CF 3）。在每种情况下，苄基 阳离子 被新戊酸酯竞争性地截获以产生 新戊酸苄酯并由苄腈产生相应的N -4-R-苄腈离子。后面的鎓离子与新戊酸酯离子反应形成苯甲二酸酐，其重排生成N -4-R-苯甲酰基-N-新戊酰基苄胺（即不对称二酰基胺）。二酰基胺的收率（R = H时最高〜10.6％）比相应的反应要小。乙腈 并且随着芳族基团上R基团的性质和位置的变化而系统地变化 核。两个电子释放和吸电子在基团对位的位置来实现diacylamine的产率的减少; 实际上，对于R ＝ NH 2，没有形成二酰基胺。芳族的邻位取代核导致二酰胺的收率大大降低，新戊酸而不是乙酸盐对腈离子的亲核攻击也是如此。因此，观察到在亲核进攻硝氮碳上的电子和空间效应。抗衡离子衍生产品与溶剂形成的苄基的衍生产物

  DOI：

  10.1039/b102014p
• 作为产物：
  描述：

  N-benzyl-2,2-dimethylpropanamide 在 sodium acetate 、 dinitrogen tetraoxide 、 sodium sulfate 作用下， 以 氯仿 为溶剂， 反应 0.42h， 以100%的产率得到N-benzyl-N-nitrosopivalamide
  参考文献：
  名称：

  通过在多个间隔物分子分离的离子对中产生的苄基阳离子进行的高效Friedel-Crafts型苄基化。

  摘要：

  脱氨作为一种高反应性碳正离子的简便方法，在有机化学，工业和医学等多个领域都受到关注。这些碳正离子的反应性和实用性源于离子对之间存在一个单独的含氮实体（N（2）或N（2）O）。我们在这里报告了一种新的脱氨基前体的合成，其亚硝化和随后的分解构成了一种新型的脱氨基方法。在这种新颖的方法中，在离子间空间中产生了多个间隔分子。所产生的阳离子具有极强的反应性，但比标准脱氨基衍生的碳阳离子具有更长的寿命。结果是，即使亲核性差的溶剂（如苯，甲苯和均三甲苯），溶剂衍生产品的产量也接近定量。

  DOI：

  10.1039/b312664a

文献信息

• N-Nitrosamide-mediated Ritter-type reactions.
  作者：Ron W. Darbeau、Rebecca S. Pease、Edson V. Perez、Rebekah E. Gibble、Faith A. Ayo、Aaron W. Sweeney

  DOI：10.1039/b204255j

  日期：2002.12.6

  Benzyl cations were generated via thermolysis of N-benzyl-N-nitrosopivalamide in molten 2-R-substituted benzonitriles (R = MeO, Me, H, F, Cl, and Br). The corresponding N-2-R-benzonitrilium species, in contrast to their 4-R-benzonitrilium counterparts, underwent limited reaction with pivalate ion to form unsymmetrical diacylamines via rearrangement of their initial imidic anhydrides. The yield of diacylamines, though small, varied systematically with the nature of the R group in a manner suggesting the operation of interesting steric and/or electronic effects on the pivalate ion-nitrilium ion collapse. The ortho-substituent, though present on only one side of the benzonitrilium ion inhibits reaction at both sides via steric hindrance in the near-ground state and steric crowding in the transition state (a “persistent steric” effect). The proposed electronic effect involves a π*-acceptor agostic-type interaction between n or σ electrons (HOMO) and the π* system (LUMO) of the nitrilium ion. Additionally, in many cases, attack by water on the nitrilium ion occurred to a significantly larger extent than attack by the much more nucleophilic and positionally favored pivalate ion on the same species. This observation is interpreted in terms of the differences in the sizes and docking trajectories of both species with the nitrilium ion due to charge and charge distribution on both nucleophiles.

  苄基阳离子是通过在熔融的2-R取代苯腈中热解N-benzyl-N-nitrosopivalamide而生成的（R = MeO, Me, H, F, Cl和Br）。与其4-R苯腈阳离子相比，相应的N-2-R苯腈阳离子与戊酸根离子的反应有限，通过其初始的亚胺酰酸酐的重排形成不对称二酰胺。尽管二酰胺的产率较低，但其随R基团性质的变化系统性地变化，这表明在戊酸根离子与苯腈阳离子的崩溃过程中，存在有趣的空间效应和/或电子效应。虽然邻位取代基仅存在于苯腈阳离子的一侧，但通过近基态的空间阻碍和过渡态的空间拥挤（“持续空间效应”）抑制了两侧的反应。提出的电子效应涉及n或σ电子（HOMO）与苯腈阳离子的π*系统（LUMO）之间的π*-接受者相互作用。此外，在许多情况下，水对苯腈阳离子的攻击显著多于位置上更有利且更具亲核性的戊酸根离子对同一物种的攻击。这一观察被解释为由于两个亲核体的电荷及其电荷分布的差异，导致它们与苯腈阳离子的大小和结合轨迹的不同。
• Boundary Conditions on the Partitioning of Deaminatively Generated Benzyl Cations
  作者：Ron W. Darbeau、Derrill J. Heurtin、Luis M. Siso、Rebecca S. Pease、Rebekah E. Gibble、Davin E. Bridges、Daneisha L. Davis、Delana G. Gbenekama、Nyla R. Darbeau

  DOI：10.1021/jo001458m

  日期：2001.4.1

  pairs (NESIPs) containing benzyl cations, nitrogen gas, and pivalate anions were generated via thermal deamination of N-benzyl-N-nitrosopivalamide. Some decompositions were performed in methanolic solutions saturated with selected nucleophiles: acetate, azide, or cyanide ions. Trace amounts of benzyl cyanide and tolunitriles were observed; no corresponding products were detected in the acetate and

  N-苄基-N-亚硝基新戊酰胺的热脱氨基反应生成了含苄基阳离子，氮气和新戊酸酯的氮原子分离离子对（NESIPs）。在用某些亲核试剂（乙酸根，叠氮化物或氰化物离子）饱和的甲醇溶液中进行了一些分解。观察到痕量的苄基氰和甲苯腈。在乙酸盐和叠氮化物的情况下，未检测到相应的产物。其他分解是在没有传统溶剂但有亲核盐的情况下进行的。再次，仅观察到阳离子对氰化物的吸收差。如果存在亲核离子，则显示效果较差，是在阳离子的寿命，有效亲核性和脱氨基笼效应的背景下讨论的。
• A Study of Electronic Effects on the Kinetics of Thermal Deamination of <i>N</i>-Nitrosoamides
  作者：Ron W. Darbeau、Rebecca S. Pease、Rebekah E. Gibble

  DOI：10.1021/jo001741l

  日期：2001.7.1

  affected by the polarity of the solvent: as the solvent polarity increased, so did the lability of the nitrosoamides. This observation of intra- and intermolecular electronic perturbations of the kinetics of nitrosoamide decomposition appears to be novel. A closer look at the rate-determining step of nitrosoamide thermolysis is made, and a mechanistic framework is proposed that accounts for both steric

  N-4-R-苄基-N-亚硝基过戊酰胺（1a-d; R = MeO，Me，H，NO（2））于18°C在C（6）D（12），CDCl（3）中分解），CD（3）CN和d（6）-DMSO的分解速率，然后用（1）H NMR光谱分析。发现亚硝基酰胺的半衰期随芳香核上R基团的性质以系统的方式变化。发现释放电子的基团降低了起始亚硝基酰胺的稳定性，而吸电子的基团提高了亚硝基酰胺的热稳定性。log（脱氨基速率常数）与sigma（p）的Hammett型图呈线性（R（2）= 0.986），rho型值为-0.90，表明在过渡过程中苄基位置上产生了明显的正电荷速率确定步骤的状态。还发现亚硝基酰胺的热稳定性受溶剂极性的系统影响：随着溶剂极性的增加，亚硝基酰胺的不稳定性也随之增加。这种对亚硝基酰胺分解动力学的分子内和分子间电子扰动的观察似乎是新颖的。仔细研究了亚硝基酰胺热解的速率确定步骤，并提出了一个机制框架，该机制考虑
• Reaction of Essentially Free Benzyl Cations with Acetonitrile; Synthesis of Ethanimidic Carboxylic Anhydrides and Unsymmetrical Diacylamines
  作者：Ron W. Darbeau、Emil H. White、Nicholas Nunez、Brian Coit、Mark Daigle

  DOI：10.1021/jo991600n

  日期：2000.2.1

  Benzyl cations were generated via the thermal decomposition of N-benzyl-N-nitrosopivalamide in acetonitrile and acetonitrile-water mixtures at 25 degrees C. The first-formed (primary) benzylating agent, the benzyl cation, was scavenged competitively by pivalate (trimethyl acetate) ion to yield benzyl pivalate, by acetonitrile to yield the corresponding N-benzylnitrilium ion, and by water (when present) to yield benzyl alcohol. The nitrilium ion underwent a cascade of reactions to yield an array of products whose identities and relative yields as a function of time were used to elucidate the mechanistic paths involved. Thus, the N-benzylnitrilium ion reacted with pivalate ion to yield the Z-isomer of N-benzylethanimidic pivalic anhydride, followed by its conversion into the E-isomer. This article appears to be the first to document compounds of this type. The E-isomer is labile under the reaction conditions, rearranging into N-acetyl-N-pivalylbenzylamine. In the presence of water as a diluent, a significant fraction of the nitrosoamide was hydrolyzed to benzyl alcohol; hydrolysis of the nitrilium ion yielded N-benzyl acetamide. The yield of hydrosylates was directly proportional to the mole fraction of water in the medium.
• Electronic Effects in the <i>N</i>-Nitrosation of <i>N</i>-Benzylpivalamides
  作者：Ron W. Darbeau、Rebecca S. Pease、Edson V. Perez

  DOI：10.1021/jo011002k

  日期：2002.5.1

  A series of N-4-R-benzylpivalamides (R = MeO, Me, H, CF3, and NO2) was nitrosated using a standardized solution of N2O4 in CDCl3 at -40 degreesC. The reactions, which produced the corresponding N-4-R-benzyl-N-nitrosopivalamides, were followed by H-1 NMR spectroscopy. The rate of nitrosation was found to vary in a systematic way with the nature of the 4-R-group on the aromatic ring. Thus, electron-releasing groups increased the rate of the reaction, whereas electron-withdrawing ones decelerated N-nitrosation. In a similar fashion, the nitrosations were accelerated in polar solvents but were slower in solvents of low polarity. The sensitivities of N-nitrosation to these intra- and intermolecular electronic effects are compared to those from a previous study examining the dependence of the kinetics of nitrosoamide thermolyses on the same factors.