N-(2-methylidenecyclopropyl)-N-nitrosourea | 312738-15-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: N-(2-methylidenecyclopropyl)-N-nitrosourea
• 英文别名: N-(methylidenecyclopropyl)-N-nitrosourea；N-(methylenecyclopropyl)-N-nitrosourea；N-(2-methylenecyclopropyl)-N-nitrosourea；1-(2-methylidenecyclopropyl)-1-nitrosourea
• CAS: 312738-15-1
• 化学式: C₅H₇N₃O₂
• mdl: MFCD19207487
• 分子量: 141.129
• InChiKey: JVHNFLPCDDTGCV-UHFFFAOYSA-N

物化性质

• 沸点：
  235.5±43.0 °C(Predicted)
• 密度：
  1.56±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  75.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(2-methylidenecyclopropyl)-N-nitrosourea 在 potassium carbonate 、 4-甲氧基苯酚 作用下， 以 二氯甲烷 为溶剂， 生成 1,2,3-丁三烯
  参考文献：
  名称：

  Azo-coupling and reduction of cyclopropanediazonium ions in the reactions with polyhydroxyarenes and aminophenols

  摘要：

  研究了环丙基重氮盐离子(由N-环丙基-N-亚硝基脲在钾或铯碳酸盐处理下分解生成)与各种多羟基芳烃和氨基苯酚的反应。偶氮偶联反应与间苯三酚、间苯二酚、3-甲氧基和3-氨基苯酚进行,生成单、双和三(环丙基偶氮)芳烃作为主要产物。可氧化的苯酚如对苯二酚、2-甲氧基、4-氨基和2-氨基苯酚会与环丙基自由基发生自由基转化反应。

  DOI：

  10.1007/s11172-008-0225-2
• 作为产物：
  描述：

  N-(methylenecyclopropyl)urea 在 硫酸 、 sodium nitrite 作用下， 以 水 为溶剂， 反应 1.25h， 以72%的产率得到N-(2-methylidenecyclopropyl)-N-nitrosourea
  参考文献：
  名称：

  Generation of diazo-2-methylenecyclopropane and its 1,3-dipolar cycloaddition to acrylates

  摘要：

  N-(2-Methylenecyclopropyl)-N-nitrosourea (2) was synthesized for the first time (yield 70%) and its decomposition induced by bases was studied. In particular, treatment with MeONa/MeOH at -30 degrees C in the presence of methyl methacrylate gives the corresponding 1-pyrazoline stereoisomers, the products of [3+2]-cycloaddition of diazo-2-methylene-cyclopropane (1) generated in situ. Decomposition of 2 on treatment with K2CO3 at 0-5 degrees C in the presence of acrylonitrile also proceeds as [3+2]-cycloaddition; however, the expected 2-pyrazoline easily isomerizes into 5(3)-isopropenyl-3(5)-cyanopyrazole. Buta-1,2,3-triene is the main product of base-induced decomposition of 2 in the absence of unsaturated substrates.

  DOI：

  10.1007/bf02495762

文献信息

• ——
  作者：I. P. Klimenko

  DOI：10.1023/a:1023910923663

  日期：——

  N-(1,3,3-Trideuterio-2-methylidenecyclopropyl)-N-nitrosourea was synthesized and its decomposition on treatment with K2CO3 in the presence of acrylonitrile and ethyl acrylate or on treatment with MeONa in the absence of unsaturated substrates was studied. The rate of decomposition of the nitrosourea is much lower than that of the nondeuterated analog. The use of acrylates for trapping the intermediate 3,3-dideuterio-1-diazo-2-methylidenecyclopropane results in the corresponding 2'-methylidenespiro[4,5-dihydropyrazole-5,1'-cyclopropanes] containing two deuterium atoms in the cyclopropane fragment. The resulting dihydropyrazoles are isomerized almost entirely over a period of 1-3 days to give a mixture (similar to1 : 1) of isopropenylpyrazoles in which both deuterium atoms occur either in the methyl or in the methylidene groups of the isopropenyl substituent. A possible mechanism of this transformation is considered.
• Azo-coupling and reduction of cyclopropanediazonium ions in the reactions with polyhydroxyarenes and aminophenols
  作者：E. V. Shulishov、I. P. Klimenko、V. A. Korolev、I. V. Kostyuchenko、G. P. Okonnishnikova、Yu. V. Tomilov

  DOI：10.1007/s11172-008-0225-2

  日期：2008.8

  A reaction of cyclopropanediazonium ion, generated by decomposition of N-cyclopropyl-N-nitrosourea upon treatment with potassium or cesium carbonates, with various poly-hydroxyarenes and aminophenols has been studied. The reaction of azo-coupling proceeds with phloroglucinol, resorcinol, 3-methoxy- and 3-aminophenol giving rise to mono-, bis-, and tris(cyclopropylazo)arenes as the major products. Oxidizable phenols such as hydro-quinone, 2-methoxy-, 4-amino-, and 2-aminophenol give products of radical transformations with participation of cyclopropyl radical.

  研究了环丙基重氮盐离子(由N-环丙基-N-亚硝基脲在钾或铯碳酸盐处理下分解生成)与各种多羟基芳烃和氨基苯酚的反应。偶氮偶联反应与间苯三酚、间苯二酚、3-甲氧基和3-氨基苯酚进行,生成单、双和三(环丙基偶氮)芳烃作为主要产物。可氧化的苯酚如对苯二酚、2-甲氧基、4-氨基和2-氨基苯酚会与环丙基自由基发生自由基转化反应。
• Generation of diazo-2-methylenecyclopropane and its 1,3-dipolar cycloaddition to acrylates
  作者：Yu. V. Tomilov、I. P. Klimenko、E. V. Shulishov、O. M. Nefedov

  DOI：10.1007/bf02495762

  日期：2000.7

  N-(2-Methylenecyclopropyl)-N-nitrosourea (2) was synthesized for the first time (yield 70%) and its decomposition induced by bases was studied. In particular, treatment with MeONa/MeOH at -30 degrees C in the presence of methyl methacrylate gives the corresponding 1-pyrazoline stereoisomers, the products of [3+2]-cycloaddition of diazo-2-methylene-cyclopropane (1) generated in situ. Decomposition of 2 on treatment with K2CO3 at 0-5 degrees C in the presence of acrylonitrile also proceeds as [3+2]-cycloaddition; however, the expected 2-pyrazoline easily isomerizes into 5(3)-isopropenyl-3(5)-cyanopyrazole. Buta-1,2,3-triene is the main product of base-induced decomposition of 2 in the absence of unsaturated substrates.