Trifluoroacetic acid → (+)-12-Oxocalanolide A

HRID 651207

반응식

HRID 651207 반응식
CC1[O:7][CH:6]([CH3:8])[O:5][CH:4]([CH3:9])O1.[O:10]1[C:19]2[C:14](=[CH:15]C=CC=2)[CH:13]=[CH:12]C1.[CH3:20][C:21]1[CH:26]=[CH:25][C:24](S([O-])(=O)=O)=[CH:23][CH:22]=1.[CH:31]1[CH:36]=[CH:35][NH+]=[CH:33][CH:32]=1.C(C(O)=[O:42])(F)(F)F.[C:44]([O-:47])(O)=O.[Na+]>ClCCCl>[CH3:33][CH2:32][CH2:31][C:36]1[C:35]2[C:23]3[O:42][C:21]([CH3:20])([CH3:22])[CH:26]=[CH:25][C:24]=3[C:44]3[O:47][C@H:13]([CH3:12])[C@@H:14]([CH3:15])[C:19](=[O:10])[C:9]=3[C:4]=2[O:5][C:6](=[O:7])[CH:8]=1

참가 물질

7

반응물 5

HCID 6422Trifluoroacetic acidHCID 9211BenzopyranHCID 31264Paraldehyde3회HCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)2회HCID 516892Sodium Bicarbonate

생성물 1

HCID 463613(+)-12-Oxocalanolide A수율 27%

시약·촉매·용매 1

HCID 111,2-Dichloroethane용매

실험 절차

Paraldehyde One-Step Reaction: To a stirring solution of chromene 4 (350 mg, 1.0 mmol) and PPTS (250 mg, 1.0 mmol) in 1,2-dichloroethane (2 mL) at ambient temperature under N2 was added 3 mL paraldehyde (22.5 mmol). The resulting mixture was refluxed for 7 h. Then, CF3CO2H (1 mL), an additional equivalent of PPTS and 1 mL of paraldehyde were added; the mixture was refluxed overnight. The reaction mixture was neutralized with saturated aqueous NaHCO3 and extracted with ethyl acetate (50 mL×3). The crude product obtained by evaporation under reduced pressure was washed with hexane. The residue was purified by column chromatography eluting with ethyl acetate/hexane (1:2) to afford 100 mg (27% yield) of chromanone (+)-7 and 30 mg (8% yield) of (+)-7a. Chromanone (+)-7 (10,11-trans-dihydro-4-propyl-6,6,10,11-tetramethyl-2H,6H,12H-benzo[1,2-b:3,4-b′:5,6-b″]tripyran-2,12-dione) obtained by this method was identical with an authentic sample by comparison of TLC, PLC and spectroscopic data.

후처리

  1. temperatureThe resulting mixture was refluxed for 7 h
  2. temperaturethe mixture was refluxed overnight
  3. extractionextracted with ethyl acetate (50 mL×3)
  4. customThe crude product obtained by evaporation under reduced pressure
  5. washwas washed with hexane
  6. customThe residue was purified by column chromatography
  7. washeluting with ethyl acetate/hexane (1:2)

출처 및 근거

ORD 기록
ord-2b777714f57241ddad68f395bb4c8974
출처 데이터셋
uspto-grants-2001_08
특허 번호
US06277879B1

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