2-(4-carboxyphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-yloxyl

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(4-carboxyphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-yloxyl
• 英文别名: 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl；2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazolidine 1-oxyl；2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxy
• 化学式: C₁₄H₁₇N₂O₃
• 分子量: 261.301
• InChiKey: PATMEXGZGWPXNA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  53.9
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  N,N’-二羟基-2,3-二甲基-2,3-丁二胺 在 sodium periodate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 27.0h， 生成 2-(4-carboxyphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-yloxyl
  参考文献：
  名称：

  Synthesis, structure and properties of benzoic acids bearing para- or meta-imino nitroxides or ortho-nitronyl nitroxide radical centres

  摘要：

  2-(4-Carboxyphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-yloxyl (p-IMBAH), 2-(3-carboxyphenyl)4,4, 5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-yloxyl (m-IMBAH) and 2-(2-carboxyphenyl)-4,4, 5,5-tetramethyl-4,5-dihydro-3-oxido-1H-imidazol-3-ium-1-yloxyl (o-NITBAH) have been prepared. The m-IM BAH and p-IMBAH radicals crystallised in monoclinic space group P2(1)/n while the o-NITBAH radical occupied the monoclinic space group Cc. In p-IMBAH, a 12-membered ring is formed via strong hydrogen bonds between two water molecules and two radicals, this unit being propagated along the b axis via additional hydrogen bonds. In m-IMBAH, the radicals are arranged in dimers held together by strong hydrogen bonds between the acid and the imine functions, each dimer being connected with its neighbours via hydrogen bonds forming alternating chains along the c axis, No cyclic arrangements are evident in o-NITBAH, the radicals being organized into;infinite chains. In each case, the product of paramagnetic susceptibility with T lies in the 0.362 to 0.374 emu K mol(-1) range at room temperature while the reciprocal susceptibility follows a Curie-Weiss law above 20 K with theta = +1.38, +5.24 and -0.81 K, respectively, for p-IMBAH, m-IMBAH and o-NITBAH. The isotropic N-14 hyperfine coupling constants are found from solution experiments to be 9.20 (a(N1)) and 4.28 (a(N2)) G for the imino radicals and 7.59 G for the nitronyl nitroxide radical. The principal values of the g-tensor measured on single crystals afforded an average of 2.0066/7 while in solution g(iso) = 2.0060 for p/m-IMBAH and 2.0065 for o-NITBAH.

  DOI：

  10.1039/a808018f

文献信息

• Structural Features of Aliphatic <i>N</i>-Nitrosamines of 7-Azabicyclo[2.2.1]heptanes That Facilitate N−NO Bond Cleavage
  作者：Tomohiko Ohwada、Motoko Miura、Haruko Tanaka、Shigeru Sakamoto、Kentaro Yamaguchi、Hirotaka Ikeda、Satoshi Inagaki

  DOI：10.1021/ja010917d

  日期：2001.10.1

  structures of N-nitrosamines, in particular of aliphatic N-nitrosamines, to the characteristics of release of NO or NO(+) remains unclear. Here we show that aliphatic N-nitrosoamines of 7-azabicyclo[2.2.1]heptanes can undergo heterolytic N-NO bond cleavage. On the basis of the observation of reduced rotational barriers of the N-NO bonds in solution and nitrogen-pyramidal structures of the N-nitroso

  N-亚硝胺可被视为潜在的一氧化氮 (NO)/亚硝基离子 (NO(+)) 供体。然而，N-亚硝胺的结构，特别是脂肪族 N-亚硝胺的结构与 NO 或 NO(+) 释放特征的关系仍不清楚。在这里，我们表明 7-氮杂双环 [2.2.1] 庚烷的脂肪族 N-亚硝基胺可以进行异裂 N-NO 键裂解。根据观察溶液中 N-NO 键的旋转势垒降低和固态 N-亚硝基的氮-锥体结构，我们假设 N-亚硝胺的 N-NO 键断裂通过减少 N-NO 基团的共振。计算研究表明 7-氮杂双环 [2.2.1] 庚烷的 N-亚硝胺的这些结构特征源自施加在 CNC 角上的角应变。
• Dendrimeric-Containing Nitronyl Nitroxides as Spin Traps for Nitric Oxide:  Synthesis, Kinetic, and Stability Studies
  作者：Gerald M. Rosen、Supatra Porasuphatana、Pei Tsai、Nicholas P. Ambulos、Valeri E. Galtsev、Kazuhiro Ichikawa、Howard J. Halpern

  DOI：10.1021/ma021292m

  日期：2003.2.1

  The in-vivo in-situ spin-trapping of NO. with iron chelates is limited in its ability to localize NO. at defined cellular compartments. Nitronyl nitroxides, such as 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl, have been found to react with NO.. The resulting nitroxide, 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazolidine 1-oxyl, exhibits an EPR spectrum that is characteristically distinct from the parent nitroxide. However, nitronyl nitroxides are unstable in biologic milieu. This limits their ability to in vivo identify NO. at specific tissue compartments. Herein, we report on the preparation of a family of dendrimer-containing nitronyl nitroxides, which were developed to spin-trap NO.. Once synthesized, we determined their rate of reaction with NO. and their capacity to spin-trap NO. and estimated the stability of dendrimer-linked nitronyl nitroxides under various experimental paradigms. For the largest of the dendrimeric nitronyl nitroxides prepared, the reaction with NO. changed the EPR spectrum from one that was broad to that with a major component with narrow and defined spectral lines. These compounds promise to be excellent biological spin-trapping agents for NO..
• On the Distinction between Nitroxyl and Nitric Oxide Using Nitronyl Nitroxides
  作者：Uri Samuni、Yuval Samuni、Sara Goldstein

  DOI：10.1021/ja101945j

  日期：2010.6.23

  A better understanding of the origins of NO and HNO and their activities and biological functions requires accurate methods for their detection and quantification. The unique reaction of NO with nitronyl nitroxides such as 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (C-PTIO), which yields the corresponding imino nitroxides, is widely used for NO detection (mainly by electron paramagnetic resonance spectroscopy) and for modulation of NO-induced physiological functions. The present study demonstrates that HNO readily reacts with nitronyl nitroxides, leading to the formation of the respective imino nitroxides and hydroxylamines via a complex mechanism. Through the use of the HNO donor Angeli's salt (AS) with metmyoglobin as a competing agent, the rate constant for C-PTIO reduction by HNO has been determined to be (1.4 +/- 0.2) x 10(5) M(-1) s(-1) at pH 7.0. This reaction yields the corresponding nitronyl hydroxylamine C-PTIO-H and NO, which is trapped by C-PTIO to form (center dot)NO(2) and the corresponding imino nitroxide, C-PTI. (center dot)NO(2) oxidizes the nitronyl and imino nitroxides to their respective oxoammonium cations, which decay mainly via comproportionation with the nitronyl and imino hydroxylamines. When [AS] > [C-PTIO], the reduction of C-PTI by HNO proceeds, eventually converting C-PTIO to the corresponding imino hydroxylamine, C-PTI-H. Similar results were obtained for 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO). It is concluded that nitronyl nitroxide is readily reduced by HNO to nitronyl hydroxylamine and is eventually converted into imino nitroxide and imino hydroxylamine. The yield of the imino hydroxylamine increases at the expense of the imino nitroxide as the ratio [AS](0)/[nitronyl nitroxide](0) is increased. Since the reaction of NO with nitronyl nitroxide yields only the corresponding imino nitroxide, nitronyl nitroxide can discriminate NO from HNO only when present at a concentration much lower than the total production of HNO.
• Synthesis, structure and properties of benzoic acids bearing para- or meta-imino nitroxides or ortho-nitronyl nitroxide radical centres
  作者：Christophe Stroh、Francisco M. Romero、Nathalie Kyritsakas、Laure Catala、Philippe Turek、Raymond Ziessel

  DOI：10.1039/a808018f

  日期：——

  2-(4-Carboxyphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-yloxyl (p-IMBAH), 2-(3-carboxyphenyl)4,4, 5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-yloxyl (m-IMBAH) and 2-(2-carboxyphenyl)-4,4, 5,5-tetramethyl-4,5-dihydro-3-oxido-1H-imidazol-3-ium-1-yloxyl (o-NITBAH) have been prepared. The m-IM BAH and p-IMBAH radicals crystallised in monoclinic space group P2(1)/n while the o-NITBAH radical occupied the monoclinic space group Cc. In p-IMBAH, a 12-membered ring is formed via strong hydrogen bonds between two water molecules and two radicals, this unit being propagated along the b axis via additional hydrogen bonds. In m-IMBAH, the radicals are arranged in dimers held together by strong hydrogen bonds between the acid and the imine functions, each dimer being connected with its neighbours via hydrogen bonds forming alternating chains along the c axis, No cyclic arrangements are evident in o-NITBAH, the radicals being organized into;infinite chains. In each case, the product of paramagnetic susceptibility with T lies in the 0.362 to 0.374 emu K mol(-1) range at room temperature while the reciprocal susceptibility follows a Curie-Weiss law above 20 K with theta = +1.38, +5.24 and -0.81 K, respectively, for p-IMBAH, m-IMBAH and o-NITBAH. The isotropic N-14 hyperfine coupling constants are found from solution experiments to be 9.20 (a(N1)) and 4.28 (a(N2)) G for the imino radicals and 7.59 G for the nitronyl nitroxide radical. The principal values of the g-tensor measured on single crystals afforded an average of 2.0066/7 while in solution g(iso) = 2.0060 for p/m-IMBAH and 2.0065 for o-NITBAH.