Triethylamine → trans-Ethyl 8-fluoro-3-phenyl-3a,4-dihydro-3h-pyrazolo[5,1-c][1,4]benzoxazine-2-carboxylate

HRID 1867263노트

반응식

HRID 1867263 반응식
Cl/[C:2](=[N:8]/[NH:9][C:10]1[CH:15]=[C:14]([F:16])[CH:13]=[CH:12][C:11]=1[O:17][CH2:18]/[CH:19]=[CH:20]/[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)/[C:3]([O:5][CH2:6][CH3:7])=[O:4].C(N(CC)CC)C.CCOC(C)=O>C1(C)C=CC=CC=1>[F:16][C:14]1[CH:13]=[CH:12][C:11]2[O:17][CH2:18][C@@H:19]3[C@H:20]([C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=4)[C:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])=[N:8][N:9]3[C:10]=2[CH:15]=1

참가 물질

5

반응물 3

HCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 89029529ethyl (2E)-2-chloro-2-[[5-fluoro-2-[(E)-3-phenylprop-2-enoxy]phenyl]hydrazinylidene]acetate

생성물 1

HCID 91552591trans-Ethyl 8-fluoro-3-phenyl-3a,4-dihydro-3h-pyrazolo[5,1-c][1,4]benzoxazine-2-carboxylate

시약·촉매·용매 1

HCID 1140Toluene용매

실험 절차

Ethyl (2E)-chloro[(5-fluoro-2-{[(2E)-3-phenylprop-2-enyl]oxy}phenyl)hydrazono]ethanoate (5-3, 3.1 g, 8.23 mmol) was dissolved in anhydrous toluene (20 mL) and treated with triethylamine (11.5 mL, 83 mmol). The reaction was heated at reflux for 24 h, and cooled. EtOAc (100 mL) was added and the organic layer was washed with 5% NaHCO3. The organic layer was dried (MgSO4), filtered and concentrated under reduced pressure. The crude was purified by flash column chromatography (120 g SiO2 Redisep, 0-30% EtOAc/hexanes gradient) to give pure trans-ethyl 8-fluoro-3-phenyl-3a,4-dihydro-3H-pyrazolo[5,1-c][1,4]benzoxazine-2-carboxylate (5-4). 1H NMR (300 MHz, CDCl3) δ 7.32 (m, 6H), 6.86 (dd, J=8.9, 5.0 Hz, 1H), 6.68 (app dt, J=7.9, 3.1 Hz, 1H), 4.34-4.12 (m, 5H), 3.62 (t, J=10.7 Hz, 1H), 1.23 (t, J=7.0 Hz, 2H); MS (M+H+, C19H17FN2O3) 340.1 found 340.4 required.

후처리

  1. temperatureThe reaction was heated
  2. temperatureat reflux for 24 h
  3. temperaturecooled
  4. washthe organic layer was washed with 5% NaHCO3
  5. dry with materialThe organic layer was dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe crude was purified by flash column chromatography (120 g SiO2 Redisep, 0-30% EtOAc/hexanes gradient)

출처 및 근거

ORD 기록
ord-3fe9cd8ca1bd42ff8980c56b7fe74c63
출처 데이터셋
uspto-grants-2009_12
특허 번호
US07632833B2

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