Trifluoroacetic acid → (+)-12-Oxocalanolide A

HRID 1637977

반응식

HRID 1637977 반응식
[CH3:1][C:2]1([CH3:25])[O:7][C:6]2[C:8]3[C:13]([CH2:14][CH2:15][CH3:16])=CC(=O)O[C:9]=3[C:18]([C:21](=[O:24])[CH2:22][CH3:23])=[C:19]([OH:20])[C:5]=2[CH:4]=[CH:3]1.[CH2:26](OC(OCC)C)[CH3:27].F[C:35](F)(F)[C:36]([OH:38])=[O:37]>C(OCC)(=O)C>[CH3:16][CH2:15][CH2:14][C:13]1[C:8]2[C:6]3[O:7][C:2]([CH3:1])([CH3:25])[CH:3]=[CH:4][C:5]=3[C:19]3[O:20][C@H:26]([CH3:27])[C@@H:22]([CH3:23])[C:21](=[O:24])[C:18]=3[C:9]=2[O:38][C:36](=[O:37])[CH:35]=1

참가 물질

5

반응물 3

HCID 6422Trifluoroacetic acidHCID 7765AcetalHCID 54948815-Hydroxy-2,2-dimethyl-6-propionyl-10-propyl-2H,8H-pyrano[2,3-f]chromen-8-one

생성물 1

HCID 463613(+)-12-Oxocalanolide A수율 30%

시약·촉매·용매 1

HCID 8857Ethyl Acetate용매

반응 조건

온도
140 °C

실험 절차

A solution containing chromene 4 (344 mg, 1.0 mmol), acetaldehyde diethylacetal (473 mg, 4.0 mmol), trifluoroacetic acid (1.5 mL, 19.4 mmol) and anhydrous pryidine (0.7 mL) was heated at 140° C. under N2. The reaction was monitored by TLC analysis. After 4 hours, the reaction mixture was cooled to room temperature, diluted with ehtyl acetate and washed several times with 10% aqueous NaHCO3 and brine. The organic layer was separated and dried over Na2SO4. The solvent was removed in vacuo and the crude product was purified by silica gel column chromatography eluting with ethyl acetate/hexane (2:3). Chromanone 7 (10,11-trans-dihydro-6,6,10,11-tetramethyl-4-propyl-2H,6H,12H-benzo[1,2-b:3,4-b':5,6-b"]-tripyran-2,12-dione) (110 mg, 30% yield) was obtained m.p. 176~177° C. (Lit.5 130~132° C.). 1H-NMR5 (CDCl3) δ 1.02 (3H, t, J=7.5 Hz, CH3); 1.21 (3H, d, J=6.8 Hz, CH3); 1.51 (3H, d, J=7.0 Hz, CH3); 1.55 (6H, 2s, 2 CH3); 1.63 (2H, sextet, J=7.0 Hz, CH2); 2.55 (1H, dq, J=6.9 Hz, J=11.0 Hz, H11); 2.88 (2H, t, J=7.6 Hz, CH2); 4.28 (1H, dq, J=6.3 Hz, J=11.0 Hz, H10); 5.60 (1H, d, J=9.9 Hz, H8); 6.04 (1H, s, H3); 6.65 (1H, d, J=11.8 Hz, H7); MS (CI): 369 (100, M+1).

후처리

  1. temperaturethe reaction mixture was cooled to room temperature
  2. washwashed several times with 10% aqueous NaHCO3 and brine
  3. customThe organic layer was separated
  4. dry with materialdried over Na2SO4
  5. customThe solvent was removed in vacuo
  6. customthe crude product was purified by silica gel column chromatography
  7. washeluting with ethyl acetate/hexane (2:3)

출처 및 근거

ORD 기록
ord-81e9fda0000d46f78da64495f4fb30d8
출처 데이터셋
uspto-grants-2000_03
특허 번호
US06043271

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