4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazole-1-oxyl-3-oxide | 802288-90-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: 4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazole-1-oxyl-3-oxide
• 英文别名: 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-ol 3-oxide；1-Hydroxy-4,4,5,5-tetramethyl-3-oxidoimidazol-3-ium
• CAS: 802288-90-0；409316-85-4
• 化学式: C₇H₁₄N₂O₂
• 分子量: 158.2
• InChiKey: IRGHOCJSYDMRIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  52.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazole-1-oxyl-3-oxide 在 selenium 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 以55%的产率得到4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazole-1-oxyl-3-oxide-2-seleno-lithium
  参考文献：
  名称：

  Electrophilic C(2)-functionalization of nitronyl nitroxides: a reference to N-heterocyclic carbenes

  摘要：

  In an attempt to generalize the recently introduced concept of 'auto-umpolung', nitronyl nitroxides are identified as precursors of a special class of electron-excess carbenes. The latter can be formally derived from nucleophilic carbenes of the Wanzlick-, Arduengo type by replacing redox-inactive N-substituents by lone-pair donor functions. A first systematic access to this class of compounds is achieved by lithiating the nitronyl nitroxide 11a at C(2), the central carbon position. The resulting radical anion equivalent 13 can be trapped in solution by various types of electrophiles to give C(2)-substituted nitronyl nitroxides 14, much in the same way as are trapped nucleophilic carbenes of the Wanzlick-Arduengo type. Carboxylation, addition to an aldehyde as well as silylation at the C(2)-position lead to novel types of functional nitronyl nitroxides. Elemental sulfur and selenium yield new types of anionic nitronyl nitroxides. The first characterized C(2)-derived heavy-metal complex of a nitronyl nitroxide 14g resulted, when Hg(OAc)(2) was used as a trapping agent. More conveniently this complex could also be obtained directly from 11a and Hg(OAc),. The X-ray structure of 14g is presented and analyzed in terms of cluster-forming secondary Hg-O interactions. 0 2001 Elsevier Science B.V. Ah rights reserved.

  DOI：

  10.1016/s0022-328x(00)00668-9
• 作为产物：
  描述：

  1,3-dihydroxy-4,4,5,5-tetramethylimidazolidine 在 manganese(IV) oxide 作用下， 以 氯仿 为溶剂， 反应 0.5h， 以75%的产率得到4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazole-1-oxyl-3-oxide
  参考文献：
  名称：

  4,5-二氢-1 H-咪唑3-氧化物与炔烃的1,3-偶极环加成反应

  摘要：

  显示在杂环的1和2位带有不同取代基的4,5-二氢-1 H-咪唑3-氧化物可与各种受体取代的炔烃反应形成相应的环加合物-1,2,3,7a衍生物-四氢咪唑并[1,2- b ]异恶唑。揭示了该过程的高区域选择性，这是由氮原子与硝酮基团的缀合所规定的。

  DOI：

  10.1002/jhet.5570430206

文献信息

• A New Class of Enehydroxylamino Ketones− (R)-2-(1-Hydroxy-4,4,5,5-tetraalkylimidazolidin-2-ylidene)ethanones: Synthesis and Reactions
  作者：Vladimir A. Reznikov、Galina I. Roshchupkina、Dmitrii G. Mazhukin、Pavel A. Petrov、Sergei A. Popov、Sergey V. Fokin、Galina V. Romanenko、Tatjana V. Rybalova、Yuri V. Gatilov、Yuri G. Shvedenkov、Irina G. Irtegova、Leonid A. Shundrin、Victor I. Ovcharenko

  DOI：10.1002/ejoc.200300536

  日期：2004.2

  Three approaches to the synthesis of (R)-2-(1-hydroxy-4,4,5,5-tetraalkylimidazolidin-2-ylidene)ethanones 1 are described: (a) condensation of 1,2-bishydroxylamines with β-ketoaldehyde synthons, (b) treatment of metallated 1-hydroxy-2-methyl-4,5-dihydroimidazoles with esters, and (c) 1,3-dipolar cycloaddition between 1-hydroxy-4,5-dihydroimidazole-3-oxide and DMAD. The reactivity of 1 with electrophiles

  描述了合成 (R)-2-(1-羟基-4,4,5,5-四烷基咪唑烷-2-亚基) 乙酮 1 的三种方法：(a) 1,2-双羟胺与 β-酮醛的缩合合成子，(b) 用酯处理金属化 1-羟基-2-甲基-4,5-二氢咪唑，和 (c) 1-羟基-4,5-二氢咪唑-3-氧化物和 DMAD 之间的 1,3-偶极环加成. 已经研究了 1 与亲电试剂的反应性。环外亚甲基（烯胺）碳原子被证明是亲电攻击的主要位点。合成的氯取代 1-羟基-2-乙炔咪唑烷与氰化钠反应形成相应的腈。这些腈的氧化伴随着持久性乙烯基氮氧化合物的形成而发生，它们作为潜在的顺磁性配体是令人感兴趣的。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany,
• Electrophilic C(2)-functionalization of nitronyl nitroxides: a reference to N-heterocyclic carbenes
  作者：Robert Weiss、Norbert Kraut、Frank Hampel

  DOI：10.1016/s0022-328x(00)00668-9

  日期：2001.1

  In an attempt to generalize the recently introduced concept of 'auto-umpolung', nitronyl nitroxides are identified as precursors of a special class of electron-excess carbenes. The latter can be formally derived from nucleophilic carbenes of the Wanzlick-, Arduengo type by replacing redox-inactive N-substituents by lone-pair donor functions. A first systematic access to this class of compounds is achieved by lithiating the nitronyl nitroxide 11a at C(2), the central carbon position. The resulting radical anion equivalent 13 can be trapped in solution by various types of electrophiles to give C(2)-substituted nitronyl nitroxides 14, much in the same way as are trapped nucleophilic carbenes of the Wanzlick-Arduengo type. Carboxylation, addition to an aldehyde as well as silylation at the C(2)-position lead to novel types of functional nitronyl nitroxides. Elemental sulfur and selenium yield new types of anionic nitronyl nitroxides. The first characterized C(2)-derived heavy-metal complex of a nitronyl nitroxide 14g resulted, when Hg(OAc)(2) was used as a trapping agent. More conveniently this complex could also be obtained directly from 11a and Hg(OAc),. The X-ray structure of 14g is presented and analyzed in terms of cluster-forming secondary Hg-O interactions. 0 2001 Elsevier Science B.V. Ah rights reserved.
• 1,3-Dipolar cycloaddition reaction of 4,5-dihydro-1<i>H</i>-imidazole 3-oxides with alkynes
  作者：Sergey A. Popov、Nikita V. Chukanov、Galina V. Romanenko、Tatjana V. Rybalova、Yuri V. Gatilov、Vladimir A. Reznikov

  DOI：10.1002/jhet.5570430206

  日期：2006.3

  4,5-Dihydro-1H-imidazole 3-oxides bearing different substituents at positions 1 and 2 of the heterocycle were shown to react with a wide range of acceptor-substituted alkynes forming corrsponding cycloadducts - derivatives of 1,2,3,7a-tetrahydroimidazo[1,2-b]isoxazole. High regioselectivity of this process stipulated by conjugation of the nitrogen atom with the nitrone group was revealed.

  显示在杂环的1和2位带有不同取代基的4,5-二氢-1 H-咪唑3-氧化物可与各种受体取代的炔烃反应形成相应的环加合物-1,2,3,7a衍生物-四氢咪唑并[1,2- b ]异恶唑。揭示了该过程的高区域选择性，这是由氮原子与硝酮基团的缀合所规定的。