1-methyl-3-propyl-5-chloro-1H-pyrazole | 29938-64-5

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: 1-methyl-3-propyl-5-chloro-1H-pyrazole
• 英文别名: 5-chloro-1-methyl-3-propyl-1H-pyrazole；5-chloro-1-methyl-3-propylpyrazole；5-chloro-1-methyl-3-propyl-1H-pyrazole；1-Methyl-3-n-propyl-5-chlorpyrazol；5-Chlor-1-methyl-3-propylpyrazol
• CAS: 29938-64-5
• 化学式: C₇H₁₁ClN₂
• 分子量: 158.631
• InChiKey: KZRXHMCRDXDCMM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  17.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-methyl-3-propyl-5-chloro-1H-pyrazole 在 2,2'-联吡啶 、 nickel(II) chloride hexahydrate 、 水 、 magnesium 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 以21%的产率得到1-methyl-3-propyl-1H-pyrazole
  参考文献：
  名称：

  Ratio of 1,3- and 1,5-dialkyl-substituted pyrazoles obtained from chlorovinyl alkyl ketones and alkylhydrazines, 3(5)-pyrazoles and alkyl bromides

  摘要：

  Unsymmetrically substituted 1,3- and 1,5-dialkylpyrazoles and 1,3-dialkyl-5-chloropyrazoles were prepared. 2-Chlorovinyl ketones react with C-1-C-8-alkylhydrazines along two routes giving mixtures of 1-R'-3-R- and 1-R'-5-R-pyrazoles with the prevalence of 1,3-isomer. The proportion of 3-substituted 1-alkylpyrazole in the isomers mixture grows from 60 to 94-97% with growing length of the alkyl chain in the hydrazine. The alkylation of 1-unsubstituted 3(5)-alkylpyrazoles with alkyl bromides afforded predominantly (by 16-50%) 1,3-disubstituted pyrazoles. 1,3-Dialkyl-5-chloropyrazoles form from 2,2-dichlorovinyl alkyl ketones and functionalized alkylhydrazines. It was suggested to synthesize 1,3-dialkyl-substituted pyrazoles by dechlorination of unsymmetrically substituted 1,3-dialkyl-5-chloropyrazoles in the presence of complex nickel catalyst and water as the proton source.

  DOI：

  10.1134/s1070428014110190
• 作为产物：
  描述：

  1,1-dichlorohex-1-en-3-one 、 偏二甲肼 以 异丙醇 为溶剂， 以77%的产率得到1-methyl-3-propyl-5-chloro-1H-pyrazole
  参考文献：
  名称：

  摘要：

  A new regioselective heterocyclization was revealed in the reaction of 2-chloro- and 2,2-dichloro(bromo)vinyl ketones with N,N-dimethylhydrazine to afford 3-substituted 1-methyl(5-halo)pyrazoles. The reaction is accompanied by elimination of methyl halide and formation of up to 90% of N,N,N-trimethylhydrazinium halide as the second product.

  DOI：

  10.1023/a:1022564707537

文献信息

• Synthesis of poly-functionalized pyrazoles under Vilsmeier-Haack reaction conditions
  作者：Aleksandr V. Popov、Valentina A. Kobelevskaya、Ludmila I. Larina、Igor B. Rozentsveig

  DOI：10.24820/ark.5550190.p010.934

  日期：——

  Synthesis of 1,3-disubstituted 5-chloro-1H-pyrazole-4-carbaldehydes was achieved by formylation of the corresponding 5-chloro-1H-pyrazoles under Vilsmeier-Haack conditions.

  1,3-二取代的 5-氯-1H-吡唑-4-甲醛的合成是通过在 Vilsmeier-Haack 条件下相应的 5-氯-1H-吡唑的甲酰化来实现的。
• Sulfonation of unsymmetrically substituted 5-chloropyrazoles
  作者：V. A. Kobelevskaya、S. G. D’yachkova、A. V. Popov、G. G. Levkovskaya

  DOI：10.1134/s1070428016060270

  日期：2016.6

  compounds for the synthesis of linear, polycyclic, and other pyrazole derivatives [1, 2]. Reactions of various alkyl(aryl)hydrazines and unsymmetrical dialkylhydrazines with 2,2-dihalovinyl ketones gave unsymmetrical 1,3-disubstituted 5-halopyrazoles which showed a low reactivity of the halogen atom toward nucleophilic substitution [1–10]. Introduction of an electron-withdrawing group (e.g., formyl, acyl, nitro

  近年来，卤代吡唑类化合物受到了广泛关注，它是合成线性、多环和其他吡唑衍生物的基础化合物 [1, 2]。各种烷基（芳基）肼和不对称二烷基肼与 2,2-二卤代乙烯基酮反应生成不对称 1,3-二取代 5-卤代吡唑，其卤素原子对亲核取代的反应性较低 [1-10]。将吸电子基团（如甲酰基、酰基、硝基等）引入 5-卤代吡唑的 4 位，可以在 5-卤原子的参与下完成反应 [1, 2, 11, 12 ]。5-氯-4-硝基吡唑与碳中心亲核试剂，特别是乙酰乙酸、芳基磺酰乙酸和氰基乙酸酯的反应，
• Synthesis and properties of 5-chloro-4-nitropyrazoles
  作者：G. V. Bozhenkov、V. A. Savosik、L. I. Larina、A. N. Mirskova、G. G. Levkovskaya

  DOI：10.1134/s1070428006060157

  日期：2006.6

  The nitration of 5-chloropyrazoles with a mixture of 100% nitric acid and 65% oleum or a mixture of 60% nitric acid and polyphosphoric acid gave substituted 5-chloro-4-nitropyrazoles in 45-91% yield. The nitration of 3-aryl-5-halopyrazoles was accompanied by introduction of a nitro group into the aromatic ring. 4-Chloropyrazoles failed to undergo nitration under these conditions. The reaction of 5-chloro-1,3-dimethyl-4-nitropyrazole with ethyl cyanoacetate in DMSO in the presence of K2CO3 led to the formation of ethyl 2-cyano-2-(1,3-dimethyl-4-nitro-1H-pyrazol-5-yl)acetate.
• ——
  作者：G. G. Levkovskaya、G. V. Bozhenkov、L. I. Larina、A. N. Mirskova

  DOI：10.1023/a:1022564707537

  日期：——

  A new regioselective heterocyclization was revealed in the reaction of 2-chloro- and 2,2-dichloro(bromo)vinyl ketones with N,N-dimethylhydrazine to afford 3-substituted 1-methyl(5-halo)pyrazoles. The reaction is accompanied by elimination of methyl halide and formation of up to 90% of N,N,N-trimethylhydrazinium halide as the second product.
• Ratio of 1,3- and 1,5-dialkyl-substituted pyrazoles obtained from chlorovinyl alkyl ketones and alkylhydrazines, 3(5)-pyrazoles and alkyl bromides
  作者：A. V. Popov、E. V. Rudyakova、L. I. Larina、V. A. Kobelevskaya、G. G. Levkovskaya

  DOI：10.1134/s1070428014110190

  日期：2014.11

  Unsymmetrically substituted 1,3- and 1,5-dialkylpyrazoles and 1,3-dialkyl-5-chloropyrazoles were prepared. 2-Chlorovinyl ketones react with C-1-C-8-alkylhydrazines along two routes giving mixtures of 1-R'-3-R- and 1-R'-5-R-pyrazoles with the prevalence of 1,3-isomer. The proportion of 3-substituted 1-alkylpyrazole in the isomers mixture grows from 60 to 94-97% with growing length of the alkyl chain in the hydrazine. The alkylation of 1-unsubstituted 3(5)-alkylpyrazoles with alkyl bromides afforded predominantly (by 16-50%) 1,3-disubstituted pyrazoles. 1,3-Dialkyl-5-chloropyrazoles form from 2,2-dichlorovinyl alkyl ketones and functionalized alkylhydrazines. It was suggested to synthesize 1,3-dialkyl-substituted pyrazoles by dechlorination of unsymmetrically substituted 1,3-dialkyl-5-chloropyrazoles in the presence of complex nickel catalyst and water as the proton source.