methanediazonium ion | 20404-06-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: methanediazonium ion
• 英文别名: diazomethane；methane-diazonium cation；Methyldiazonium-Ion；Methyldiazoniumion；Methanediazonium
• CAS: 20404-06-2
• 化学式: CH₃N₂
• 分子量: 43.0482
• InChiKey: RRJZCACJJKZDNV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  methanediazonium ion 在 氪气 作用下， 生成 methylkryptonium
  参考文献：
  名称：

  由离子回旋共振甲基阳离子转移平衡确定的甲基rypto离子中的碳-键强度

  摘要：

  DOI：

  10.1021/j100301a028
• 作为产物：
  描述：

  (E)-methanediazoate 在 sodium perchlorate 作用下， 以 异丙醇 为溶剂， 生成 methanediazonium ion
  参考文献：
  名称：

  Rate-Limiting Formation of Diazonium Ions in the Aqueous Decomposition of Primary Alkanediazoates

  摘要：

  Rate constants, k(0), for the buffer-independent decomposition of four primary (E)-alkanediazoates and one primary (Z)-alkanediazoate in aqueous media at 25 degrees C, ionic strength 1 M (NaClO4) are reported. Between pH 4 and 12 the plot of log k(0) against pH is biphasic with a hydrogen ion-dependent reaction at the high-pH end changing to a pH-independent region at lower pH. The change in absorbance at 235 nm of the relatively stable (E)-trifluoroethanediazoate as a function of pH gives a good fit to a simple titration curve for a monofunctional acid with pK(a) = 7.00 +/- 0.04 that is in good agreement with the kinetic pK(a) determined from the pH-rate profile between pH 4 and 12. The plot of log k(1), the pH-independent rate constant, against sigma* for the primary (E)-alkanediazoates, and (E)-methane- and (E)-2-butanediazoates previously reported, yields a common line with a slope rho* = -4.4. Of the 1-butanol formed from the decomposition of (E)-1-butanediazoate in D2O at pH(obs),b, = 10.50, 6% contains deuterium, while, of the 1-butanol formed in the presence of 1 M NaOD in D2O, 25% contains deuterium. A total of 96% of the iodotrifluoroethane formed upon decomposition of (E)-trifluoroethanediazoate in a D2O solution that is 1 M in NaI contains at least a single deuterium atom. These data combined with small negative values of Delta S#, normal solvent deuterium isotope effects, and the decreases in k(1) of between 500- and 1000-fold on change of solvent to ethanol are consistent with a mechanism that involves the rate-limiting unassisted heterolytic bond fission of the diazoic acid to yield the diazonium ion. The decomposition of [O-16]-(E)-1-butanediazoate in water containing 47 +/- 2% O-18 yields 1-butanol of which 49 +/- 2% contains O-18. This observation, in combination with the observed pH-dependent deuterium incorporation into 1-butanol during decomposition of (E)-1-butanediazoate, above, indicates that the 1-butanediazonium ion is a diffusionally equilibrated intermediate. The rate constant for the pH-independent decomposition of the (Z)-trifluoroethanediazoate is 2600 times greater than that for the corresponding (E) isomer. The decomposition of the (Z)-trifluoroethanediazoate, but not its (E) isomer, is catalyzed by buffer acids, and the catalysis by carboxylic acids is characterized by a Bronsted plot with a slope alpha = 0.41. Catalysis by methoxylammonium ion is comparatively weak, the rate constant falling a log unit below the aforementioned Bronsted line. The solvent deuterium isotope effect for formic acid catalysis is k(HA)/k(DA) = 3.1 +/- 0.2 It is concluded that the mechanism for general acid catalysis of the decomposition of the (Z)-diazoic acid entails proton transfer to oxygen that is concerted with N-O bond heterolysis to yield the diazonium ion.

  DOI：

  10.1021/ja00094a016
• 作为试剂：
  描述：

  二氧化碳 、 2,4-dimethoxy-5-lithiopyrimidine 在 methanediazonium ion 作用下， 生成 2,4-二甲氧基嘧啶-5-甲酸甲酯
  参考文献：
  名称：

  Synthesis of 5-Substituted Pyrimidines through ortho-Directed Lithiation Reactions

  摘要：

  DOI：

  10.3987/r-1987-03-0585

文献信息

• [EN] PYRIMIDINE PDE10 INHIBITORS<br/>[FR] INHIBITEURS PYRIMIDINES DE PDE10
  申请人：MERCK SHARP & DOHME

  公开号：WO2013028590A1

  公开（公告）日：2013-02-28

  The present invention is directed to pyrimidine compounds which are useful as therapeutic agents for the treatment of central nervous system disorders associated with phosphodiesterase 10 (PDE10). The present invention also relates to the use of such compounds for treating neurological and psychiatric disorders, such as schizophrenia, psychosis or Huntington's disease, and those associated with striatal hypofunction or basal ganglia dysfunction.

  本发明涉及嘧啶化合物，其可用作治疗与磷酸二酯酶10（PDE10）相关的中枢神经系统疾病的治疗剂。本发明还涉及利用这些化合物治疗神经系统和精神疾病，如精神分裂症、精神病或亨廷顿病，以及与纹状体功能不足或基底神经节功能障碍相关的疾病。
• [EN] PHENYLPYRIDAZINE DERIVATIVES AS LIGANDS FOR GABA RECEPTORS<br/>[FR] DERIVES DE PHENYLPYRIDAZINE UTILISES EN TANT QUE LIGANDS POUR DES RECEPTEURS GABA
  申请人：MERCK SHARP & DOHME

  公开号：WO2004014865A1

  公开（公告）日：2004-02-19

  A class of 4-phenylpyridazine derivatives of Formula (I), being selective ligands for GABAA receptors, in particular having high affinity for the α2 and/or α3 and or α5 subunit thereof, are accordingly of benefit in the treatment and/or prevention of adverse conditions of the central nervous system, including anxiety, convulsions and cognitive disorders.

  Formula (I)的4-苯基吡啶并衍生物是GABAA受体的选择性配体，特别是对其α2和/或α3和/或α5亚基具有高亲和力，因此在治疗和/或预防中枢神经系统的不良状况，包括焦虑、抽搐和认知障碍方面具有益处。
• Specific acid catalysis in the decomposition of trialkyltriazenes
  作者：Christopher J. Michejda、Cheryl L. Denlinger、Robert Kupper、Steven R. Koepke、Richard H. Smith

  DOI：10.1021/ja00316a040

  日期：1984.2

  On etudie les decompositions des triazenes R−N=N−NR'R'' (R=R'=C 4 H 9 , R''=CH 3 ; R=R'=R''=CH 3 ; R=R'=CH 3 , R''=COCH 3 ; R=R'=CH 3 , R''=CO 2 C 2 H 5 )

  关于三氮烯分解研究 R−N=N−NR'R'' (R=R'=C 4 H 9 , R''=CH 3 ; R=R'=R''=CH 3 ; R=R '=CH 3 ，R''=COCH 3 ；R=R'=CH 3 ，R''=CO 2 C 2 H 5 )
• Convenient synthesis of 1,4-thiazane-3-carboxylic acid derivatives.
  作者：KAZUO SAKAI、NAOTO YONEDA

  DOI：10.1248/cpb.29.1554

  日期：——

  A convenient method to synthesize 1, 4-thiazane-3-carboxylic acid derivatives was established. Condensation of L-cysteine methyl ester (2a) with monochloroacetone (3a) followed by reduction with sodium borohydride yielded methyl (3R, 5S)-5-methyl-1, 4-thiazane-3-carboxylate (6a) and its (5R)-methyl isomer (7a) in a ratio of 3.1 : 1. The use of cysteine isopropyl ester (2c) instead of methyl ester (2a) gave the corresponding (5S)-methyl isomer (6e) more stereoselectively. The reaction of chloromethyl ethyl ketone (3b) or α-bromoacetophenone (3c) with 2a gave the corresponding 5-substituted-1, 4-thiazane-3-carboxylates. Hydrolysis and oxidation of 6a yielded cycloalliin (1a).

  建立了一种合成 1，4-噻嗪-3-羧酸衍生物的简便方法。L-半胱氨酸甲酯（2a）与一氯丙酮（3a）缩合，然后用硼氢化钠还原，得到(3R, 5S)-5-甲基-1, 4-噻嗪-3-羧酸甲酯（6a）及其(5R)-甲基异构体（7a），两者的比例为 3.1 ：1.使用半胱氨酸异丙酯 (2c) 代替甲酯 (2a)，可以更立体选择性地得到相应的 (5S)- 甲基异构体 (6e)。氯甲基乙基酮（3b）或α-溴苯乙酮（3c）与 2a 反应生成相应的 5-取代-1，4-噻嗪-3-羧酸盐。6a 经水解和氧化后得到环木菠萝苷 (1a)。
• Protonation of diazomethane in superacid media
  作者：John F. McGarrity、D. Phillip Cox

  DOI：10.1021/ja00350a037

  日期：1983.6