Water → HCID 13453490, compound

HRID 846863Notes

Reaction equation

HRID 846863 reaction equation
[CH3:1][O:2][C:3]1[C:12]2[C:7](=[C:8]([O:13][CH3:14])[CH:9]=[CH:10][CH:11]=2)[C:6]([O:15][CH3:16])=[C:5]([CH2:17][CH:18]2[CH2:23][CH2:22][C:21]([CH:25](O)[CH3:26])([OH:24])[CH2:20][CH:19]2[C:28]([O:30]CC2C=CC=CC=2)=O)[CH:4]=1.C(OC(=O)C)(=O)C.N1C=CC=CC=1.[K+].[Br-].[OH2:53]>CN(C)C1C=CN=CC=1>[OH:53][CH:25]([C:21]1([OH:24])[CH2:22][CH2:23][CH:18]2[CH:19]([C:28](=[O:30])[C:4]3[C:5]([CH2:17]2)=[C:6]([O:15][CH3:16])[C:7]2[C:12](=[CH:11][CH:10]=[CH:9][C:8]=2[O:13][CH3:14])[C:3]=3[O:2][CH3:1])[CH2:20]1)[CH3:26]

Participants

7

Reactant 5

HCID 962WaterHCID 1049PyridineHCID 7918Acetic AnhydrideHCID 253877Potassium BromideHCID 13453489HCID 13453489, compound

Product 1

HCID 13453490HCID 13453490, compoundYield 49%

Reagents, catalysts & solvents 1

HCID 142844-(Dimethylamino)pyridineCatalyst

Procedure

0.48 g of 1-(1,4,5-trimethoxy-3-naphthylmethyl)-2-benzyloxycarbonyl-4-(1-hydroxyethyl)-4-hydroxy-cyclohexane, prepared as described in Example 5, was treated with acetic anhydride and pyridine in the presence of 4-dimethylamino-pyridine. After a night at room temperature the reaction mixture was poured into iced water and extracted with ethyl acetate. The organic layer was washed with water and concentrated. The crude product was dissolved in methanol and refluxed with cyclohexene in the presence of 10% by weight palladium-on-carbon. The catalyst was then filtered off and the solution, concentrated to a small volume, was treated at 0° C. for 60 minutes with trifluoroacetic anhydride and trifluoroacetic acid. Then the solution was diluted with ethyl acetate, washed with an aqueous saturated solution of sodium bicarbonate and with water, dried and concentrated to dryness under vacuum. The residue was dissolved in methanol in the presence of catalytic amount of sodium methylate. After conventional work-up and purification by chromatography 0.18 g of the title compound was obtained (yield 49%): m/z 400 (M+.); IR (KBr): 3450 cm-1 (OH), 1675 cm-1 (C=O benzylic ketone); PMR (CDCl3): inter alia δ (1.2 (d, CH3 --CH), 3.7-3.9 (s, three OCH3) and 6.4-8.0 (m, three aromatic hydrogen).

Workup

  1. extractionextracted with ethyl acetate
  2. washThe organic layer was washed with water
  3. concentrationconcentrated
  4. dissolutionThe crude product was dissolved in methanol
  5. temperaturerefluxed with cyclohexene in the presence of 10% by weight palladium-on-carbon
  6. filtrationThe catalyst was then filtered off
  7. concentrationthe solution, concentrated to a small volume
  8. additionwas treated at 0° C. for 60 minutes with trifluoroacetic anhydride and trifluoroacetic acid
  9. additionThen the solution was diluted with ethyl acetate
  10. washwashed with an aqueous saturated solution of sodium bicarbonate and with water
  11. customdried
  12. concentrationconcentrated to dryness under vacuum
  13. dissolutionThe residue was dissolved in methanol in the presence of catalytic amount of sodium methylate
  14. customAfter conventional work-up and purification by chromatography 0.18 g of the title compound
  15. customwas obtained (yield 49%)

Sources & evidence

ORD record
ord-f1c18e30d2f74cb28c26255cbc2a209d
Source dataset
uspto-grants-1992_08
Patent number
US05138042

Reaction notes

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