1-Methoxy-2-oxo-3,3-diethyl-1-triazene | 112753-63-6

• 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: 1-Methoxy-2-oxo-3,3-diethyl-1-triazene
• 英文别名: (Z)-diethylamino-methoxyimino-oxido-ammonium；(Z)-diethylamino-methoxyimino-oxidoazanium
• CAS: 112753-63-6；138833-23-5
• 化学式: C₅H₁₃N₃O₂
• 分子量: 147.177
• InChiKey: RRVPABSEZXWXNU-VURMDHGXSA-N

物化性质

• 沸点：
  179.5±23.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  53.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-Methoxy-2-oxo-3,3-diethyl-1-triazene 以 乙腈 为溶剂， 生成 甲醇 、 聚合甲醛 、 乙醛肟 、 N-亚硝基二乙胺
  参考文献：
  名称：

  Diazeniumdiolates 的化学。3. 光反应

  摘要：

  我们发现 O(2)-取代的二氮烯二醇盐，结构为 R(2)NN(O)=NOR' 的化合物，正在开发用于各种可能的药物用途，具有相当的光敏性。当 R = 乙基且 R' = 甲基、苄基或 2-硝基苄基时，观察到的产物分布表明有两个主要途径在起作用。一个次要途径涉及一氧化二氮 (N(2)O) 的挤出，同时生成 R(2)N(*) 和 R'O(*)，然后可能形成胺、醛和醇。主要的反应途径是 N=N 键的有趣光化学裂解，形成亚硝胺 (R(2)NN=O) 和氧取代的氮烯 (R'ON)。通过将 O-硝烯重排为 C-亚硝基化合物 (R'ON --> O=NR')，可以从大量肟的产生中推断出 O-硝烯的中间体，和随后的互变异构化为更稳定的肟。通过用 2,3-二甲基-2-丁烯捕获形成氮丙啶并用氧捕获生成硝酸酯，证实了 O-氮烯的参与。苄基衍生物上的 2-硝基取代对反应过程几乎没有影响。对于所检测的每种化合物，都观察到了少量的一氧化氮

  DOI：

  10.1021/ja002898y
• 作为产物：
  描述：

  3-氯苯甲酰乙腈 、 N-亚硝基二乙胺 在 lead(IV) acetate 、 potassium carbonate 作用下， 生成 1-Methoxy-2-oxo-3,3-diethyl-1-triazene
  参考文献：
  名称：

  Artsybasheva, Yu. P.; Ioffe, B. V., Journal of Organic Chemistry USSR (English Translation), 1987, p. 1056 - 1060

  摘要：

  DOI：

文献信息

• Preparation and Reactivity of <i>O</i>²-Sulfonated Diazeniumdiolates
  作者：Raechelle A. D'Sa、Yuhong Wang、Patrick H. Ruane、Brett M. Showalter、Joseph E. Saavedra、Keith M. Davies、Michael L. Citro、Melissa N. Booth、Larry K. Keefer、John P. Toscano

  DOI：10.1021/jo026656n

  日期：2003.1.1

  We report the facile preparation of O-2-sulfonated diazeniumdiolates and mechanistic investigation of their reactions with representative nucleophiles. This new class of compounds extends the range of O-2-substituted diazeniumdiolates available for potential applications in research and medicine.
• Secondary amine/nitric oxide complex ions, R2N[N(O)NO]-. O-Functionalization chemistry
  作者：Joseph E. Saavedra、Tambra M. Dunams、Judith L. Flippen-Anderson、Larry K. Keefer

  DOI：10.1021/jo00049a017

  日期：1992.11

  Alkylation of the R2N[N(O)NO]- anion has been studied with the aim of extending the reaction's scope, probing its stereochemistry, and exploring the reactivity of its variously functionalized products. Using the sodium salt of the R = Et ion (1) as the standard starting material, numerous novel products having the structure Et2N[N2O2]R]' (2) were isolated from its reaction with alkyl halides, sulfate esters, and oxiranes. In addition to previously described examples in which R' is a simple straight-chain alkyl or benzyl group, new compound types in which R' is hydroxylated, halide-containing, alpha-methoxylated, and olefinic were prepared. The 2-bromoethyl derivative could be dehydrohalogenated to the O-vinyl compound or further reacted with other nucleophiles such as amines, water, or a second mole of 1 to produce additional new compound types. Ethylation of 1 appeared to occur exclusively at the terminal oxygen to give Et2NN(O)=NOEt as the only isomer detected; this conclusion regarding the regiochemistry of the reaction conflicts with that found in the previous literature, but its generality was supported by X-ray crystallographic analysis of the Et2NN(O)=NOCH2CH2(NC5H5)+Br- analogue. Hydrolytic decomposition of 2 was slow, even for the O-vinyl and -methoxymethyl derivatives, as reflected in the sluggish loss of the intense chromophore these compounds characteristically show at 225-245 nm (epsilon (6.5-9) x 10(3) M-1 cm-1); half-lives at 37-degrees-C for the latter two compounds were 12 h in 0.1 M HCl and 9 h in 1 M HCl respectively. N-Nitrosodiethylamine was a frequent byproduct of both the synthesis and hydrolysis of 2. The results should aid the effort to design prodrug derivatives of 1, a compound type which has recently been shown to exhibit useful pharmacological effects.
• Artsybasheva, Yu. P.; Ioffe, B. V., Journal of Organic Chemistry USSR (English Translation), 1987, p. 1056 - 1060
  作者：Artsybasheva, Yu. P.、Ioffe, B. V.

  DOI：——

  日期：——
• Chemistry of the Diazeniumdiolates. 3. Photoreactivity
  作者：Aloka Srinivasan、Naod Kebede、Joseph E. Saavedra、Alexander V. Nikolaitchik、Daniel A. Brady、Emily Yourd、Keith M. Davies、Larry K. Keefer、John P. Toscano

  DOI：10.1021/ja002898y

  日期：2001.6.1

  R' = methyl, benzyl, or 2-nitrobenzyl, the observed product distributions suggest that two primary pathways are operative. A minor pathway involves the extrusion of nitrous oxide (N(2)O) with simultaneous generation of R(2)N(*) and R'O(*), which may then form amines, aldehydes, and alcohols. The major reaction pathway is an interesting photochemical cleavage of the N=N bond to form a nitrosamine (R(2)NN=O)

  我们发现 O(2)-取代的二氮烯二醇盐，结构为 R(2)NN(O)=NOR' 的化合物，正在开发用于各种可能的药物用途，具有相当的光敏性。当 R = 乙基且 R' = 甲基、苄基或 2-硝基苄基时，观察到的产物分布表明有两个主要途径在起作用。一个次要途径涉及一氧化二氮 (N(2)O) 的挤出，同时生成 R(2)N(*) 和 R'O(*)，然后可能形成胺、醛和醇。主要的反应途径是 N=N 键的有趣光化学裂解，形成亚硝胺 (R(2)NN=O) 和氧取代的氮烯 (R'ON)。通过将 O-硝烯重排为 C-亚硝基化合物 (R'ON --> O=NR')，可以从大量肟的产生中推断出 O-硝烯的中间体，和随后的互变异构化为更稳定的肟。通过用 2,3-二甲基-2-丁烯捕获形成氮丙啶并用氧捕获生成硝酸酯，证实了 O-氮烯的参与。苄基衍生物上的 2-硝基取代对反应过程几乎没有影响。对于所检测的每种化合物，都观察到了少量的一氧化氮