Hydrochloric Acid → 3-Methyl-1-(2,4,6-trichlorophenyl)-1H-pyrazol-5-amine

HRID 612979

反応式

HRID 612979 の反応式
[Na].CC1ON=CC=1.ClC1C=C(Cl)C=C(Cl)C=1NN.Cl.[Cl:20][C:21]1[CH:26]=[C:25]([Cl:27])[CH:24]=[C:23]([Cl:28])[C:22]=1[NH:29][N:30]=[C:31]([CH3:35])[CH2:32][C:33]#[N:34].C[O-].[Na+]>CO.O.CCOCC>[NH2:34][C:33]1[N:29]([C:22]2[C:21]([Cl:20])=[CH:26][C:25]([Cl:27])=[CH:24][C:23]=2[Cl:28])[N:30]=[C:31]([CH3:35])[CH:32]=1

参加物

10

反応物 6

HCID 313Hydrochloric AcidHCID 79234(2,4,6-Trichlorophenyl)hydrazineHCID 798335-MethylisoxazoleHCID 5360545Sodium2 回HCID 10942334Sodium MethoxideHCID 865850181-Cyanoacetone-2,4,6-trichlorophenylhydrazone

生成物 1

HCID 20600323-Methyl-1-(2,4,6-trichlorophenyl)-1H-pyrazol-5-amine

試薬・触媒・溶媒 3

HCID 887Methanol溶媒4 回HCID 962Water溶媒HCID 3283Diethyl Ether溶媒

実験手順

To a solution of 0.51 g (22.0 mmol) of sodium in methanol was added 1.66 g (20.0 mmol) of 5-methylisoxazole. The reaction mixture as refluxed for 8 hours and then stirred overnight at room temperature. Then 4.23 g (20.0 mmol) of 2,4,6-trichlorophenylhydrazine was added and the reaction mixture was again refluxed for 4 hours. A second portion of sodium In methanol was added and reflux was continued for 24 hours. The reaction mixture was taken up with ether and dilute hydrogen chloride. The organic extracts were washed with dilute hydrogen chloride and brine, and then dried with magnesium sulfate and evaporated to give crystals, m.p. 132-134° C. Analysis of this material, particularly two CN bands in the IR spectrum at 2190 cm-1 and 2250 cm-1, revealed it to be a mixture of the cis- and trans-isomers of 1-cyanoacetone-2,4,6-trichlorophenylhydrazone. This material was suspended in methanol and treated with 10.0 mmol of sodium methoxide in 5 mL of methanol. After 5 minutes at room temperature, water was added to crystallize the product which was filtered off and washed well with water. After air drying, the product weighed 2.21 g (40%) and melted at 134.0-135.5° C. Despite the similarity in melting points, the latter material was distinctly different from the former, having an R1 of 0.67 vs. 0.78 for the intermediate on silica gel TLC plates developed with 1:1 hexane ethyl acetate and a distinctly different 300 MHz proton NMR spectrum.

後処理

  1. temperatureThe reaction mixture as refluxed for 8 hours
  2. temperaturethe reaction mixture was again refluxed for 4 hours
  3. temperaturereflux
  4. waitwas continued for 24 hours
  5. washThe organic extracts were washed with dilute hydrogen chloride and brine
  6. dry with materialdried with magnesium sulfate
  7. customevaporated
  8. customto give crystals, m.p. 132-134° C
  9. waitAfter 5 minutes at room temperature
  10. customto crystallize the product which
  11. filtrationwas filtered off
  12. washwashed well with water
  13. customAfter air drying

出典と根拠

ORDレコード
ord-5371c3b5d71942d593e0134c9ac21e95
出典データセット
uspto-grants-1999_12
特許番号
US06005109

関連ノート

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