nitrosocarbonylmethane | 63115-45-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: nitrosocarbonylmethane
• 英文别名: N-Oxoacetamide
• CAS: 63115-45-7
• 化学式: C₂H₃NO₂
• 分子量: 73.0513
• InChiKey: CMKOFJHXSRPTJX-UHFFFAOYSA-N

物化性质

• 沸点：
  72.7±23.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-甲基-1-苯基丙烯 、 nitrosocarbonylmethane 生成 N-hydroxy-N-(2-methyl-1-phenylprop-2-enyl)acetamide
  参考文献：
  名称：

  烯丙基酰胺化。亚硝基羰基甲烷对烯烃直接烯丙基官能化的研究

  摘要：

  亚硝基羰基甲烷通过烯途径与多种烯烃反应，在制备上有用的反应中产生N-取代的异羟肟酸产物。对于不对称烯烃，可以通过涉及将氮亲电加成到烯烃中的机理来合理化观察到的区域化学偏好。

  DOI：

  10.1016/s0040-4039(01)86667-3
• 作为产物：
  描述：

  acetyl radical 在 氧气 、 氧化亚氮 、 六氟化硫 作用下， 以 gas 为溶剂， 21.85 ℃ 、100.0 kPa 条件下， 生成 nitrosocarbonylmethane
  参考文献：
  名称：

  Absolute rate constants for F + CH3CHO and CH3CO + O2, relative rate study of CH3CO + NO, and the product distribution of the F + CH3CHO reaction

  摘要：

  DOI：

  10.1002/(sici)1097-4601(1998)30:12<913::aid-kin6>3.0.co;2-5

文献信息

• Photogeneration and reactivity of acyl nitroso compounds
  作者：Anthony S. Evans、Andrew D. Cohen、Zachary A. Gurard-Levin、Naod Kebede、Tevye C. Celius、Alexander P. Miceli、John P. Toscano

  DOI：10.1139/v10-101

  日期：2011.2

  Acyl nitroso compounds have been generated by photolysis of several different classes of precursors including 9,10-dimethylanthracene adducts, nitrodiazo compounds, and 1,2,4-oxadiazole-4-oxides. Consideration of the nitronate-like resonance structure of nitrodiazo compounds led to an examination of the photochemistry of nitronates with α-leaving groups. Photolysis of such nitronates has been shown to generate an acyl nitroso species along with a carbene intermediate. Nanosecond time-resolved infrared (TRIR) spectroscopy has been used to detect photogenerated acyl nitroso compounds directly and to examine their reaction kinetics with amines and thiols. The mechanism of acyl nitroso aminolysis by primary amines involves general base catalysis, while the mechanism of aminolysis by secondary amines is strictly bimolecular. Thiols do not seem to be reactive with acyl nitroso compounds on the microsecond time scale, but thiolates are quite reactive. The reaction between benzoyl nitroside and an organic-soluble thiolate, tetrabutylammonium dodecanethiolate, proceeds via a proposed tetrahedral intermediate, which is observable by TRIR spectroscopy.

  通过光解几类不同的前体（包括 9,10-二甲基蒽加合物、硝基重氮化合物和 1,2,4-恶二唑-4-氧化物）生成了酰基亚硝基化合物。考虑到硝基重氮化合物的类似硝酸酯的共振结构，我们对带有 α 离去基团的硝酸酯的光化学进行了研究。研究表明，此类硝酸酯的光解会产生一种酰基亚硝基物种和一种碳烯中间体。纳秒时间分辨红外光谱（TRIR）被用来直接检测光生成的酰基亚硝基化合物，并研究它们与胺和硫醇的反应动力学。伯胺对酰基亚硝基化合物进行氨解的机理涉及一般碱催化，而仲胺对酰基亚硝基化合物进行氨解的机理则是严格的双分子机理。在微秒时间尺度上，硫醇似乎不会与亚硝基酰基化合物发生反应，但硫代硫酸酯却具有相当高的反应活性。亚硝酸苯甲酰与一种有机可溶的硫醇酸盐，即十二硫酸四丁基铵之间的反应是通过一种拟议的四面体中间体进行的，这种中间体可通过 TRIR 光谱观察到。
• A mild oxidation method of hydroxamic acids: efficient trapping of acyl nitroso intermediates
  作者：Seiji Iwasa、Kentaro Tajima、Shinji Tsushima、Hisao Nishiyama

  DOI：10.1016/s0040-4039(01)01119-4

  日期：2001.8

  Ruthenium(II)-pyridine-2,6-dicarboxylate (pydic) of 2,6-bis(oxazolinyl)pyridine (pybox-dh) complex catalyzed the hydrogen peroxide oxidation of hydroxamic acid in the presence of cyclopentadiene to give acyl nitroso cycloadducts in 74–99% yield.

  2,6-双（恶唑啉基）吡啶（pybox-dh）络合物的钌（II）-吡啶-2,6-二羧酸酯（吡啶基）在环戊二烯存在下催化异羟肟酸的过氧化氢氧化，从而制得酰基亚硝基环加合物产率74–99％。
• Nitrosocarbonyl release from O-substituted hydroxamic acids with pyrazolone leaving groups
  作者：Saghar Nourian、Robert P. Lesko、Daryl A. Guthrie、John P. Toscano

  DOI：10.1016/j.tet.2016.08.016

  日期：2016.10

  acids with pyrazolone leaving groups (OHPY), is described. These compounds generate nitrosocarbonyl intermediates, which upon hydrolysis release nitroxyl (azanone, HNO) under physiologically relevant conditions. Pyrazolones have been used to confirm the generation of nitrosocarbonyls by competitive trapping to form isomeric N-substituted hydroxamic acids (NHPY) via an N-selective nitrosocarbonyl aldol reaction

  描述了一种新的亚硝基羰基前体，具有吡唑啉酮离去基团（OHPY）的O-取代的异羟肟酸。这些化合物生成亚硝基羰基中间体，该中间体水解后在生理上相关的条件下释放出硝酰基（氮杂酮，HNO）。吡唑啉酮已被用于通过竞争性捕集经由N-选择性的亚硝基羰基醛醇缩合反应形成异构体的N-取代的异羟肟酸（NHPY）来确认亚硝基羰基的生成。OHPY供体的亚硝基羰基释放速率受供体取代基（包括吡唑啉酮离去基团）的影响。
• Straightforward hetero Diels–Alder reactions of nitroso dienophiles by microreactor technology
  作者：Jean-Christophe M.R. Monbaliu、Ana Cukalovic、Jacqueline Marchand-Brynaert、Christian V. Stevens

  DOI：10.1016/j.tetlet.2010.08.117

  日期：2010.11

  The hetero Diels-Alder reactions of 2-nitrosotoluene and some representative acylnitrosodienophiles with a selected set of 1,3-dienes were studied under microflow conditions. The main assets of the technology, that is, an accurate control of the reaction parameters and continuous operating, led to an increased efficiency of this reaction. (C) 2010 Elsevier Ltd. All rights reserved.
• Synthesis of the Antimalarial Drug FR900098 Utilizing the Nitroso-Ene Reaction
  作者：Andrey A. Fokin、Alexander G. Yurchenko、Vladimir N. Rodionov、Pavel A. Gunchenko、Raisa I. Yurchenko、Armin Reichenberg、Jochen Wiesner、Martin Hintz、Hassan Jomaa、Peter R. Schreiner

  DOI：10.1021/ol702082k

  日期：2007.10.1

  The antimalarial drug FR900098 was prepared from diethyl allylphosphonate involving the nitroso-ene reaction with nitrosocarbonyl methane as the key step followed by hydrogenation and dealkylation. The utilization of dibenzyl allylphosphonate as the starting compound allows one-step hydrogenation with dealkylation, which simplifies the preparative scheme further.