Methane, dichloromethoxy- → 5-(4-isobutyl-4H-[1,2,4]triazol-3-yl)-2,4-dimethoxy-benzaldehyde

HRID 10735

반응식

HRID 10735 반응식
[CH3:1][O:2][C:3]1[CH:8]=[C:7]([O:9][CH3:10])[CH:6]=[CH:5][C:4]=1[C:11]1[N:15]([CH2:16][CH:17]([CH3:19])[CH3:18])[CH:14]=[N:13][N:12]=1.[CH3:20][O:21]C(Cl)Cl>[Ti](Cl)(Cl)(Cl)Cl>[CH2:16]([N:15]1[CH:14]=[N:13][N:12]=[C:11]1[C:4]1[C:3]([O:2][CH3:1])=[CH:8][C:7]([O:9][CH3:10])=[C:6]([CH:5]=1)[CH:20]=[O:21])[CH:17]([CH3:19])[CH3:18]

참가 물질

4

반응물 2

HCID 21004Methane, dichloromethoxy-HCID 219810123-(2,4-dimethoxy-phenyl)-4-isobutyl-4H-[1,2,4]triazole

생성물 1

HCID 219810255-(4-isobutyl-4H-[1,2,4]triazol-3-yl)-2,4-dimethoxy-benzaldehyde수율 28%

시약·촉매·용매 1

HCID 24193Titanium Tetrachloride촉매

반응 조건

온도
0 °C

실험 절차

Ex-109E: To a solution of 3-(2,4-dimethoxy-phenyl)-4-isobutyl-4H-[1,2,4]triazole (Ex-109D, 0.78 g, 2.98 mmol) was added dichloromethyl methyl ether (0.4 mL, 4.48 mmol) followed by addition of titanium tetrachloride (1.0M in dichloromethane, 9.0 mL, 9.0 mmol) over 10 min at 0° C. The reaction mixture was allowed to stir at 0° C. for 30 min and ambient temperature overnight. The reaction mixture was poured into ice. The aqueous solution was extracted with dichloromethane and isopropyl alcohol (33%, v/v, in dichloromethane). The combined dichloromethane and isopropyl alcohol were washed with brine, dried over sodium sulfate and concentrated. The aqueous solution was treated with sodium hydroxide to pH 12 and extracted again with isopropyl alcohol (33%, v/v, in dichloromethane) to give additional product. The crude product was purified by flash chromatography. Elution with methanol (10%, v/v, in dichloromethane) afford 5-(4-isobutyl-4H-[1,2,4]triazol-3-yl)-2,4-dimethoxy-benzaldehyde (0.24 g, 28%): 1H NMR (CDCl3) δ 10.30 (s, 1H), 8.17 (s, 1H), 7.90 (s, 1H), 6.51 (s, 1H), 4.00 (s, 3H), 3.87 (s, 3H), 3.58 (d, J=7.2 Hz, 2H), 1.91–1.80 (m, 1H), 0.77 (d, J=6.5 Hz, 6H).

후처리

  1. additionThe reaction mixture was poured into ice
  2. extractionThe aqueous solution was extracted with dichloromethane and isopropyl alcohol (33%, v/v, in dichloromethane)
  3. washThe combined dichloromethane and isopropyl alcohol were washed with brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. additionThe aqueous solution was treated with sodium hydroxide to pH 12
  7. extractionextracted again with isopropyl alcohol (33%, v/v, in dichloromethane)
  8. customto give additional product
  9. customThe crude product was purified by flash chromatography
  10. washElution with methanol (10%, v/v, in dichloromethane)

출처 및 근거

ORD 기록
ord-bfb8c66bff4d48099a2e5ecf4d4ad3f8
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07094801B2

연결된 노트

불러오는 중…