N-(2-甲基苯基)-N-甲基亚硝基胺 | 10596-01-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: N-(2-甲基苯基)-N-甲基亚硝基胺
• 英文名称: N-methyl-N-nitroso-o-toluidine
• 英文别名: 2-Methyl-N-nitroso-N-methyl-anilin；2,N-Dimethyl-N-nitroso-anilin；N-Nitroso-N-methyl-o-toluidin；Dimethyl-nitrosoaniline；N-methyl-N-(2-methylphenyl)nitrous amide
• CAS: 10596-01-7
• 化学式: C₈H₁₀N₂O
• 分子量: 150.18
• InChiKey: MWHUIOFIRPAVBJ-UHFFFAOYSA-N

物化性质

• 沸点：
  89-90 °C(Press: 1.5 Torr)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  32.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(2-甲基苯基)-N-甲基亚硝基胺 在 silver hexafluoroantimonate 、 dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 氯化铵 、 溶剂黄146 、 锌 作用下， 以 甲醇 为溶剂， 反应 10.0h， 生成 (E)-methyl 3-(3-methyl-2-(methylamino)phenyl)acrylate
  参考文献：
  名称：

  一种通用的，无痕量的基于C H活化的杂环合成方法

  摘要：

  据报道，一种通用的，无痕量的基于C H活化的方法可合成各种杂环。在室温下，Rh（III）催化的，N-氨基定向的C–H烯基化反应会以原子经济和分步经济的方式生成烯化产物或吲哚（原位环化）。该引导基团赋予的显着反应性使得能够在非常低的催化剂负载量（0.01 mol％/ 0.1 mol％）下将反应规模扩大至10 g规模。烯化产物的异位环化提供进入一系列杂环的入口。

  DOI：

  10.1021/acs.orglett.6b00949
• 作为产物：
  描述：

  邻甲苯胺 在 盐酸 、 水 、 sodium nitrite 作用下， 生成 N-(2-甲基苯基)-N-甲基亚硝基胺
  参考文献：
  名称：

  Historical development and characteristics of social work in today’s China

  摘要：

  Social work education has experienced three stages since its introduction to China in the 1920s: introduction, abolishment and reinstatement. Theoretically, there are four types of social work in China: official–educational, official–practical, voluntary–educational and voluntary–practical. In practice, all four types of social work have not necessarily been embodied in each developmental stage, and the order of their historical development is not the same as the order of their logical development; i.e. some types are lacking in some of the stages. Each type of social work has its own characteristics, which are integrated into each development stage. Today, Chinese social work faces two major interrelated tasks: the professionalisation and the institutionalisation of social work. The former refers to the development of standardisation in Chinese social work; the latter has to do with the development of the social welfare institution in general and the development of institutional welfare in particular. In general, the dramatic development in Chinese social work largely depends on the accomplishment of the two tasks.

  DOI：

  10.1111/1468-2397.00222

文献信息

• Rhodium(III)-Catalyzed Directed C−H Amidation of <i>N</i> -Nitrosoanilines and Subsequent Formation of 1,2-Disubstituted Benzimidazoles
  作者：Yanyu Chen、Rong Zhang、Qiujun Peng、Lanting Xu、XianHua Pan

  DOI：10.1002/asia.201701287

  日期：2017.11.2

  An efficient rhodium‐catalyzed direct C−H amidation of N‐nitrosoanilines with 1,4,2‐dioxazol‐5‐ones as amidating agents has been developed. This method featured mild reaction conditions, a wide substrate scope and satisfactory yields. Besides, the amidated products could be readily converted to pharmaceutically valuable 1,2‐disubstituted benzimidazoles via an HCl‐mediated deprotection/cyclization process

  已经开发了一种高效的铑催化的N-亚硝基苯胺的直接CH H酰胺化反应，使用1,4,2-二恶唑5-1作为酰胺化剂。该方法的特点是反应条件温和，底物范围广且产率令人满意。此外，酰胺化的产品可以在一个锅中通过HCl介导的脱保护/环化过程轻易地转化为具有药用价值的1,2-二取代的苯并咪唑。
• Palladium-catalyzed decarboxylative ortho-acylation of N-nitrosoanilines with α-oxocarboxylic acids
  作者：Jia-Ping Yao、Guan-Wu Wang

  DOI：10.1016/j.tetlet.2016.03.009

  日期：2016.4

  A palladium-catalyzed efficient C–H acylation reaction of N-nitrosoanilines with α-oxocarboxylic acids has been developed. The reaction proceeded smoothly with potassium persulfate as the oxidant to afford acylated N-nitrosoanilines in moderate to good yields with a broad substrate scope and good regioselectivity.

  已开发出钯催化的N-亚硝基苯胺与α-氧代羧酸的高效C–H酰化反应。反应以过硫酸钾为氧化剂进行得很顺利，以中等到良好的收率得到酰化的N-亚硝基苯胺，具有广泛的底物范围和良好的区域选择性。
• Palladium-catalyzed ortho-acylation of N-Nitrosoanilines with α-oxocarboxylic acids: a convenient method to synthesize N-Nitroso ketones and indazoles
  作者：Liang Zhang、Zhe Wang、Peiyu Guo、Wei Sun、Ya-Min Li、Meng Sun、Chengwen Hua

  DOI：10.1016/j.tetlet.2016.04.096

  日期：2016.6

  An efficient and mild protocol for regioselective synthesis of N-Nitroso aryl ketones by palladium-catalyzed direct acylation of arenes using N-Nitroso as directing groups is described. This reaction proceeded smoothly and could tolerate a variety of functional groups. Moreover, this chemistry offers a convenient access to a range of indazoles.

  描述了一种有效且温和的方案，用于使用N-亚硝基作为导向基团，通过钯催化的芳烃直接酰化区域选择性地合成N-亚硝基芳基酮。该反应进行顺利，并且可以耐受多种官能团。此外，这种化学方法可方便地获得各种吲唑。
• Palladium-Catalyzed Decarboxylative Acylation of <i>N</i>-Nitrosoanilines with α-Oxocarboxylic Acids
  作者：Yinuo Wu、Lei Sun、Yunyun Chen、Qian Zhou、Jia-Wu Huang、Hui Miao、Hai-Bin Luo

  DOI：10.1021/acs.joc.5b02535

  日期：2016.2.5

  A palladium-catalyzed oxidative C–H bond decarboxylative acylation of N-nitrosoanilines using α-oxocarboxylic acid as the acyl source is described. The catalyst Pd(OAc)2 and oxidant (NH4)2S2O8 enabled ortho-acylation of N-nitrosoanilines at room temperature, affording an array of N-nitroso-2-aminobenzophenones in moderate to excellent yields.

  描述了使用α-氧代羧酸作为酰基源的钯催化的N-亚硝基苯胺的氧化C–H键脱羧酰化反应。催化剂Pd（OAc）2和氧化剂（NH 4）2 S 2 O 8可以在室温下对N-亚硝基苯胺进行邻酰化，从而以中等至极好的收率提供了一系列N-亚硝基-2-氨基二苯甲酮。
• Reactions of cyclopalladated N-nitrosoanilines with SnIV reagents. Crystal structure of the bis cyclopalladated complex cis-Pd{ONN(CH3)(C6H4)}2
  作者：Alberto Albinati、Samuel Affolter、Paul S. Pregosin

  DOI：10.1016/0022-328x(90)85281-3

  日期：1990.9

  N(1)-Pd-C(2) = 79.5(2); C(2)-Pd-C(9) = 102.4(2). It is suggested that the formation of a specific coordination sphere, involving, one cyclometallated ligand, one weakly coordinated ligand, and a monodentate carbon ligand, such as CH3, leads to production of 5.

  一系列的环钯Ñ甲基Ñ -nitrosoanilines，[钯（μ-X）ONN（CH 3）（C 6 H ^ 3 Y）}] 2，X = OAC，氯，Y = 4-OCH 3，4 -CH 3，4-NO 2，5-CH 3，已经制备并用（I）的各种试剂，得到单核钯（II）的衍生物，和（ii）R的1 3 SNR 2，以最终得到2- R 2取代了N-甲基-N-亚硝基苯胺。锡（IV）试剂中，Me 4 Sn的中，Me 3 SnCCPh，卜3Ñ SnCC（CH 2）4 CH 3，卜3 Ñ SnCHCH 2和Bu 3 Ñ SNCH 2 CHCH 2所有有效R传送2组的Pd，但，转移反应的机制不一定都是一样的。在某些情况下，需要存在其他配体，例如PPh 3或（Ph 2 PCH 2）2来抑制副反应，尤其是双环钯配合物顺式-Pd ONN（CH 3）（C 6 H）的形成。4）} 2，5。5的晶体结构已通过X射