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

HRID 2400526노트

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HRID 2400526 반응식
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

참가 물질

4

반응물 2

HCID 88600Methyl acetopyruvateHCID 45074960HCID 45074960, 화합물

생성물 1

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

시약·촉매·용매 1

HCID 176Acetic Acid용매

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온도
90 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-7964a4cacec94f8dabeb778be8f8a92b
출처 데이터셋
uspto-grants-2014_08
특허 번호
US08796253B2

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