Sodium Sulfite → 9-cis-4-Oxoretinoic acid

HRID 1584293노트

반응식

HRID 1584293 반응식
[CH3:1][C:2]1[CH:7]([OH:8])[CH2:6][CH2:5][C:4]([CH3:10])([CH3:9])[C:3]=1/[CH:11]=[CH:12]/[C:13](/[CH3:23])=[CH:14]\[CH:15]=[CH:16]\[C:17](\[CH3:22])=[CH:18]\[C:19]([OH:21])=[O:20].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.C([O-])(O)=O.[Na+].[O-]S([O-])=O.[Na+].[Na+]>C(Cl)Cl.CCOCC>[CH3:1][C:2]1[C:7](=[O:8])[CH2:6][CH2:5][C:4]([CH3:9])([CH3:10])[C:3]=1/[CH:11]=[CH:12]/[C:13](/[CH3:23])=[CH:14]\[CH:15]=[CH:16]\[C:17](\[CH3:22])=[CH:18]\[C:19]([OH:21])=[O:20]

참가 물질

7

반응물 4

HCID 24437Sodium SulfiteHCID 159087TriacetoxyperiodinaneHCID 516892Sodium BicarbonateHCID 20849244HCID 20849244, 화합물

생성물 1

HCID 99729399-cis-4-Oxoretinoic acid수율 90%

시약·촉매·용매 2

HCID 3283Diethyl Ether용매HCID 6344Dichloromethane용매

실험 절차

To a solution of 4-hydroxy-9-cis-retinoic acid (16 mg, 0.05 mmole) in CH2Cl2 (1.5 ml) was added Dess-Martin reagent [see Dess and Martin in J. Org. Chem. 48:4155 (1983)] (42 mg, 0.1 mmole) in one portion at 25° C. After stirring for 5 minutes, the mixture was diluted with 10 ml of ether and to this was added saturated aqueous NaHCO3 (5 ml) containing Na2SO3 (55 mg). The mixture was stirred for 20 minutes to dissolve the solid and the layers separated. The ether layer was washed with H2O (2×5 ml), brine (5 ml) and dried (MgSO4). The solvent was recovered under reduced pressure and residue was subjected to flash column chromatography (silica, 60% ether in Hexane) to give 4-keto-9-cis-retinoic acid (14 mg. 90%), characterized as follows: TLC rf=0.6 (silica, 80% ether in hexane); 1HNMR (400 mHz, CDCl3) δ 7.05 (dd, J=16, 12 Hz, 1H, olefinic), 6.82 (d, J=16 Hz, 1H, olefinic), 6.32 (d, J=16 Hz, 1H, olefinic), 6.30 (d, J=16 Hz, 1H, olefinic), 6.20 (d, J=12 Hz, 1H, olefinic), 5.80 (s, 1H, olefinic), 2.5 (t, J=7 Hz, 2H, CH2 --CO), 2.31 (s, 3H, CH3), 2.01 (s, 3H, CH3), 1.9 (s, 3H, CH3), 1.89 (m, 2H, CH2), 1.20 (s, 6H, 2×CH3).

후처리

  1. stirringThe mixture was stirred for 20 minutes
  2. dissolutionto dissolve the solid
  3. customthe layers separated
  4. washThe ether layer was washed with H2O (2×5 ml), brine (5 ml)
  5. dry with materialdried (MgSO4)
  6. customThe solvent was recovered under reduced pressure and residue

출처 및 근거

ORD 기록
ord-01033b861d0646ba8f9bf87af18add86
출처 데이터셋
uspto-grants-1999_08
특허 번호
US05932622

반응 노트

불러오는 중…