4-甲基-1,2,4-三唑 | 10570-40-8

• 物质功能分类: 医药中间体 - 杂环化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 中文名称: 4-甲基-1,2,4-三唑
• 中文别名: 4-甲基-1,2,4-三氮唑
• 英文名称: 4-methyl-4H-[1,2,4]triazole
• 英文别名: 4-methyl-1,2,4-triazole；4-Methyl-1,2,4-triazol；1-methyl-1,3,4-triazole；4-Methyl-4H-1,2,4-triazole
• CAS: 10570-40-8
• 化学式: C₃H₅N₃
• mdl: MFCD00490021
• 分子量: 83.0928
• InChiKey: XILPCSMEKCBYFO-UHFFFAOYSA-N

物化性质

• 熔点：
  90-92℃
• 沸点：
  175℃
• 密度：
  1.17
• 闪点：
  60℃

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.333
• 拓扑面积：
  30.7
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2933990090
• 危险性防范说明：
  P280,P305+P351+P338,P310
• 危险性描述：
  H302,H315,H319,H332,H335
• 储存条件：
  2-8°C，干燥密封保存。

反应信息

• 作为反应物：
  描述：

  4-甲基-1,2,4-三唑 在 diclazuril 作用下， 生成
  参考文献：
  名称：

  Zaydoun; Idrissi; Garrigou-Lagrange, Canadian Journal of Chemistry, 1987, vol. 65, # 11, p. 2509 - 2512,2509-2512

  摘要：

  DOI：
• 作为产物：
  描述：

  4-甲基-4H-3-巯基-1,2,4-三氮唑 以85%的产率得到
  参考文献：
  名称：

  PAPADOPOULOS E. P.; SCHUPBACH C. M., J. ORG. CHEM., 1979, 44, NO 1, 99-104

  摘要：

  DOI：

文献信息

• Radical Deoxygenation of Xanthates and Related Functional Groups with New Minimalist N-Heterocyclic Carbene Boranes
  作者：Shau-Hua Ueng、Louis Fensterbank、Emmanuel Lacôte、Max Malacria、Dennis P. Curran

  DOI：10.1021/ol101015m

  日期：2010.7.2

  Minimalist N-heterocyclic carbene boranes 1,3-dimethylimidazol-2-ylideneborane and 2,4-dimethyl-1,2,4-triazol-3-ylideneborane are readily available and have low molecular weights. They exhibit superior performance to first-generation NHC−boranes, providing improved yields in reductions of xanthates and related functional groups.

  极简主义的N-杂环卡宾硼烷1,3-二甲基咪唑-2-亚基硼烷和2,4-二甲基-1,2,4-三唑-3-亚基硼烷很容易获得，并且分子量低。它们表现出优于第一代NHC-硼烷的性能，在减少黄药和相关官能团方面提供了更高的收率。
• Synthesis and Crystal Structures of New 1,4-Disubstituted 1,2,4-Triazoline-5-thiones
  作者：Gerhard Laus、Volker Kahlenberg、Klaus Wurst、Herwig Schottenberger

  DOI：10.5560/znb.2014-4145

  日期：2014.10.1

  Introduction of sulfur into the 5-position of 1,4-disubstituted quaternary 1,2,4-triazolium salts (1-9; Cl, Br, I, BF₄, PF₆, CH₃OSO₃ were used as anions) by two methods was investigated. The syntheses of nine 1,4-disubstituted 1,2,4-triazoline-5-thiones 10-18 are reported (1, 10: R¹ = CH₃, R² = CH₃; 2, 11: R¹ = NH₂, R² = CH₃; 3, 12: R¹ = NH₂, R² = CH(CH₃)₂; 4, 13: R¹ = N(CH₃)₂, R² = CH₃; 5, 14: R¹ = N(CH₃)₂, R² = CH(CH₃)₂; 6, 15: R¹ = CH₃, R² = NH₂; 7, 16: R¹ = OCH₂Ph, R² = CH₃; 8, 17: R¹ = OCH₂Ph, R² = CH₂CH₃; 9, 18: R¹ = CH₃, R² = CH₂Ph). Compounds 11-17 represent 1-amino, 4-amino, 4-dimethylamino, and 4-benzyloxy-1,2,4-triazoline-5- thiones, whereas 10 served as a reference compound. Thione 18 was identified as an unexpected by-product in the synthesis of 16 and was also prepared independently. Thermolysis of 10 in air gave 1,4-dimethyl-1,2,4-triazolium hydrogensulfate. Crystal structures of eight 1,4-disubstituted 1,2,4- triazoline-5-thiones were determined by single-crystal X-ray diffraction. Intermolecular hydrogen bonds (C-H···S, C-H···N, N-H···N, N-H···S) were observed in the solid state. The solvent-dependent ¹H NMR chemical shifts of signals of 10 and 13 were satisfactorily correlated with the Kamlet- Abboud-Taft π* and b parameters in ten solvents. From the lack of correlation with the a parameter and from the C=S bond length (average 1.67 Å) a significant contribution of a mesoionic imidazolium-2-thiolate resonance structure seems unlikely

  摘要 通过两种方法研究了在 1,4-二取代季态 1,2,4-三唑鎓盐 (1-9; Cl, Br, I, BF4, PF6, CH3OSO3 被用作阴离子) 的 5 位引入硫。报告了九种 1,4-二取代的 1,2,4-三唑啉-5-硫代化合物 10-18 的合成（1, 10：R1 = CH3，R2 = CH3；2, 11：R1 = NH2，R2 = CH3；3, 12：R1 = NH2，R2 = CH(CH3)2；4, 13：4，13：R1 = N（CH3）2，R2 = CH3；5，14：R1 = N（CH3）2，R2 = CH（CH3）2；6，15：R1 = CH3，R2 = NH2；7，16：R1 = OCH2Ph，R2 = CH3；8，17：R1 = OCH2Ph，R2 = CH2CH3；9，18：R1 = CH3，R2 = CH2Ph）。化合物 11-17 代表 1-氨基、4-氨基、4-二甲基氨基和 4-苄氧基-1,2,4-三唑啉-5-硫酮，而 10 则作为参比化合物。硫酮 18 是在合成 16 的过程中意外发现的副产品，也是独立制备的。10 在空气中热解得到 1,4-二甲基-1,2,4-三唑鎓氢硫酸盐。通过单晶 X 射线衍射测定了 8 种 1,4 二甲基-1,2,4-三唑啉-5-硫酮的晶体结构。在固态下观察到了分子间氢键（C-H--S、C-H--N、N-H--N、N-H--S）。在十种溶剂中，10 和 13 信号的溶剂依赖型 1H NMR 化学位移与 Kamlet- Abboud-Taft π* 和 b 参数的相关性令人满意。从与 a 参数缺乏相关性和 C=S 键长度（平均 1.67 Å）来看，介离子咪唑鎓-2-硫酸酯共振结构似乎不可能做出重大贡献。
• Alkanoylation of quinazoline by nucleophilic aromatic substitution: Combined experimental and computational study
  作者：Yumiko Suzuki、Naoto Iwata、Kohei Dobashi、Ryo Takashima、Sundaram Arulmozhiraja、Erika Ishitsubo、Naoya Matsuo、Hiroaki Tokiwa

  DOI：10.1016/j.tet.2017.11.071

  日期：2018.1

  A combined experimental and computational study on the key intermediates of NHC-catalyzed acylation reaction, Breslow intermediates (BIs), has been conducted in order to achieve a direct nucleophilic alkanoylation of N-heterocycles. Various BI precursors are alternatively prepared and used in the reaction with 4-chloroquinazoline. The present study reveals that the intermediates having benzimidazole

  为了实现N杂环的直接亲核烷酰基化，已对NHC催化的酰化反应的关键中间体Breslow中间体（BIs）进行了组合的实验和计算研究。或者制备各种BI前体并将其用于与4-氯喹唑啉的反应中。本研究表明具有苯并咪唑部分的中间体用作引入直链烷酰基的酰化剂。自然键轨道分析表明中间体的反应性与πC -C的占有率部分相关羟基烯胺部分的键。从理论上研究了酰化反应的推定速率确定步骤。使用BI前体合成了几种新的4-烷酰基喹唑啉。
• 氮杂环双卡宾亚基硼烷类离子液体及其制备方法
  申请人：南京工业大学

  公开号：CN108250227A

  公开（公告）日：2018-07-06

  本发明涉及一种氮杂环双卡宾亚基硼烷类离子液体及其制备方法。所述氮杂环双卡宾亚基硼烷类离子液体的结构如式I所示。制备式I所示化合物的方法，其主要步骤是：由1,2,4‑三氮唑和碳酸酯类化合物通过烷基化反应，再与卤代烃发生季胺化反应，最后与硼氢化钠反应，得到目标产物。本发明所提供的离子液体可以用作自燃型绿色火箭推进剂燃料，具有点火延迟时间短，水稳定性好，密度比冲值大等优势。式I中，R1选自烷基中的任意一种；R2选自烃基取代基中的任意一种。
• Spin-transition behaviour in chains of FeII bridged by 4-substituted 1,2,4-triazoles carrying alkyl tails
  作者：Olivier Roubeau、Jose´ M. Alcazar Gomez、Emily Balskus、Jeroen J. A. Kolnaar、Jaap G. Haasnoot、Jan Reedijk

  DOI：10.1039/b007094g

  日期：——

  A family of polymeric 1-dimensional chains of iron(II) species showing the spin-crossover phenomenon has been synthesized using 4-n-alkyl-1,2,4-triazoles as bridging ligands. The influence of the length of the alkyl tails on the triazole ligands on characteristic features of the spin transition was studied, showing degrading of steepness with increasing length. A set of four counter ions has been used to access a wider range of transition temperatures. Large hysteresis loops are detected with small tails, mainly for the methyl and ethyl substituted products. In most cases longer tails weaken co-operativity and hysteresis gradually decreases to zero. However it is shown that with certain anions hysteresis remains, even with very long tails on the triazoles. Weakening of the co-operativity mainly arises from a diminution of the length of the polymeric chains with increasing alkyl tails on the triazole. This effect is anion dependent. A strong interaction along the polymeric chains is confirmed.

  合成了一种聚合物一维链的铁(II)物种，表现出自旋跨越现象，采用4-n-烷基-1,2,4-三唑作为桥联配体。研究了烷基尾巴长度对三唑配体自旋跃迁特征的影响，发现随着烷基尾巴长度的增加，自旋跃迁的陡峭度降低。使用了一组四种对离子，以获取更广泛的跃迁温度范围。检测到小尾巴的样品存在较大的滞回环，主要是甲基和乙基取代的产物。在大多数情况下，较长的尾巴削弱了协同作用，滞回现象逐渐减小至零。然而，研究表明，对于某些阴离子，即使在三唑上有很长的尾巴，滞回现象仍然存在。协同作用的减弱主要源于随着三唑上的烷基尾巴增大，聚合物链的长度减少。这个效应依赖于阴离子。确认了聚合物链之间存在强相互作用。

表征谱图