Methyl acetopyruvate → 1H-Pyrazole-3-carboxylic acid, 5-methyl-1-[(4-methylphenyl)methyl]-, methyl ester

HRID 2400526

反応式

HRID 2400526 の反応式
Cl.Cl.[CH3:3][C:4]1[CH:12]=[CH:11][C:7]([CH2:8][NH:9][NH2:10])=[CH:6][CH:5]=1.[CH3:13][C:14]([CH2:16][C:17]([C:19]([O:21][CH3:22])=[O:20])=O)=O>C(O)(=O)C>[CH3:13][C:14]1[N:9]([CH2:8][C:7]2[CH:11]=[CH:12][C:4]([CH3:3])=[CH:5][CH:6]=2)[N:10]=[C:17]([C:19]([O:21][CH3:22])=[O:20])[CH:16]=1

参加物

4

反応物 2

HCID 88600Methyl acetopyruvateHCID 45074960HCID 45074960、化合物

生成物 1

HCID 595046501H-Pyrazole-3-carboxylic acid, 5-methyl-1-[(4-methylphenyl)methyl]-, methyl ester収率 45%

試薬・触媒・溶媒 1

HCID 176Acetic Acid溶媒

反応条件

温度
90 °C

実験手順

A mechanically stirred suspension of 4-(methylbenzyl)hydrazine dihydrochloride (Step 3, 81.8 g, 391 mmol) and methyl acetopyruvate (51.2 g, 356 mmol) in acetic acid (825 mL) was warmed to 90° C. and stirred for 4 h. The solid gradually dissolved, leaving an orange solution. After being cooled to rt, the reaction mixture was concentrated to an orange oil. The organic residue was diluted with EtOAc, washed with water (1×250 mL), NaHCO3 (1×250 mL), and brine (1×250 mL), was dried (Na2SO4), filtered and concentrated to an orange oil. Purification with an ISCO CombiFlash Companion, using a gradient from 0% to 30% EtOAc in hexanes afforded the title compound as a yellow-orange oil (39 g, 45%): 1H NMR (300 MHz, d6-DMSO) δ 2.20 (s, 3H), 2.24 (s, 3H), 3.75 (s, 3H), 5.31 (s, 2H), 6.56 (s, 1H), 7.01 (d, 2H), 7.12 (d, 2H). ES-MS m/z 245.0 (MH)+, HPLC RT (Method A) 3.13 min.

後処理

  1. dissolutionThe solid gradually dissolved
  2. customleaving an orange solution
  3. temperatureAfter being cooled to rt
  4. concentrationthe reaction mixture was concentrated to an orange oil
  5. additionThe organic residue was diluted with EtOAc
  6. washwashed with water (1×250 mL), NaHCO3 (1×250 mL), and brine (1×250 mL)
  7. dry with materialwas dried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated to an orange oil
  10. customPurification with an ISCO CombiFlash Companion

出典と根拠

ORDレコード
ord-7964a4cacec94f8dabeb778be8f8a92b
出典データセット
uspto-grants-2014_08
特許番号
US08796253B2

関連ノート

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