Methanol → 1-Butyl-5-[2-(2-methoxycarbonylphenylmethoxy)-4methoxyphenyl]-1h-pyrazole

HRID 1265163노트

반응식

HRID 1265163 반응식
C(N(CC)/[CH:4]=[CH:5]/[C:6]([C:8]1[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][C:9]=1[O:10][CH2:11][C:12]1[CH:21]=[CH:20][CH:19]=[CH:18][C:13]=1[C:14]([O:16][CH3:17])=[O:15])=O)C.CO.C([O-])(=O)C.[Na+].C(O)(=O)C(O)=O.[CH2:43]([NH:47][NH2:48])[CH2:44][CH2:45][CH3:46]>CC(OC)(C)C.O>[CH2:43]([N:47]1[C:6]([C:8]2[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][C:9]=2[O:10][CH2:11][C:12]2[CH:21]=[CH:20][CH:19]=[CH:18][C:13]=2[C:14]([O:16][CH3:17])=[O:15])=[CH:5][CH:4]=[N:48]1)[CH2:44][CH2:45][CH3:46]

참가 물질

7

반응물 4

HCID 887MethanolHCID 162021Butylhydrazine oxalateHCID 517045Sodium AcetateHCID 11058397(e)-Methyl 2-[[2-[3-(diethylamino)-1-oxo-2-propenyl]-5-methoxyphenoxy]methyl]benzoate

생성물 1

HCID 108945201-Butyl-5-[2-(2-methoxycarbonylphenylmethoxy)-4methoxyphenyl]-1h-pyrazole수율 104.8%

시약·촉매·용매 2

HCID 962Water용매HCID 15413tert-Butyl methyl ether용매

실험 절차

To a 5 L round bottomed flask was added (E)-methyl 2-[[2-[3-(diethylamino)-1-oxo-2-propenyl]-5-methoxyphenoxy]methyl]benzoate (150 g, 0.37 mol), 2.9 L of methanol and 0.45 L of water. After complete dissolution, a premixed quantity of sodium acetate (294 g, 3.58 mol) and n-butylhydrazine oxalate salt (133 g, 0.746 mol) was added via a powder funnel in rapid portions over a period of 20 minutes. The reaction mixture was blanketed with nitrogen during the reaction period. After 20 hours the reaction mixture was partitioned between 3 L of ethyl acetate and 3 L of water. The aqueous was removed and poured into 2 L of ethyl acetate and the aqueous was separated once again. This operation was repeated once more with 1.2 L of ethyl acetate (a total of 6 L of ethyl acetate used in total). The combined organic extracts were dried (magnesium sulfate) and concentrated under reduced pressure to 187 g of a thick oil. Flash chromatography (50% TBME/Hex) afforded the title compound (153 g, 73% yield) as a colourless oil which slowly solidified on standing: 1H NMR (300 MHz, CDCl3) δ 8.02 (1H, d), 7.6 (1H, d), 7.52-7.22 (3H, m), 7.12 (1H, d), 6.64 (1H, d), 6.54 (1H, dd), 6.20 (1H, s), 5.48 (2H, s), 4.01 (2H, t), 3.89 (s 3H), 3.76 (3H, s), 1.7-1.5 (2H, m), 1.2-1.05 (2H, m), 0.7 (3H, t).

후처리

  1. dissolutionAfter complete dissolution
  2. customThe reaction mixture was blanketed with nitrogen during the reaction period
  3. customAfter 20 hours the reaction mixture was partitioned between 3 L of ethyl acetate and 3 L of water
  4. customThe aqueous was removed
  5. additionpoured into 2 L of ethyl acetate
  6. customthe aqueous was separated once again
  7. dry with materialThe combined organic extracts were dried (magnesium sulfate)
  8. concentrationconcentrated under reduced pressure to 187 g of a thick oil

출처 및 근거

ORD 기록
ord-47cc7f4cfe384adfa5962fd08956a649
출처 데이터셋
uspto-grants-2003_04
특허 번호
US06545031B1

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