Water → HCID 10895779, compound

HRID 1699460Notes

Reaction equation

HRID 1699460 reaction equation
[C:1]12([C:11](Cl)=[O:12])[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.[CH3:14][C:15]([C:17]1[CH:22]=[C:21]([OH:23])[CH:20]=[CH:19][C:18]=1[OH:24])=[O:16].O>N1C=CC=CC=1>[C:1]12([C:11]([O:23][C:21]3[CH:22]=[C:17]4[C:18](=[CH:19][CH:20]=3)[O:24][C:11]([C:1]35[CH2:10][CH:5]6[CH2:4][CH:3]([CH2:9][CH:7]([CH2:6]6)[CH2:8]3)[CH2:2]5)=[CH:14][C:15]4=[O:16])=[O:12])[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2

Participants

5

Reactant 3

HCID 962WaterHCID 102792-AcetylhydroquinoneHCID 989151-Adamantanecarbonyl chloride

Product 1

HCID 10895779HCID 10895779, compound

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

4 g 1-adamantoyl chloride are added to a solution of 1.5 g 2,5-dihydroxyacetophenone in dry pyridine. The mixture is stirred for 18 hours at 40°, poured into water and extracted with ethyl acetate. The combined organic layers are washed 3 times with 1 N aqueous hydrochloric acid and subsequently with aqueous sodium carbonate solution, dried over magnesium sulfate and concentrated in vacuo. The crude product is dissolved in dry dimethylformamide and added dropwise at 5° to a suspension of 330 mg of sodium hydride (80% in mineral oil) in dry dimethylformamide. The cooling bath is removed, and the mixture is stirred for 4 hours at room temperature. Then 1.5 ml of acetic acid and 250 ml of water are added, followed by extraction with ethyl acetate. The combined extracts are dried over magnesium sulfate and evaporated in vacuo. The residue is chromatographed on silica gel (cyclohexane/ethyl acetate 6/1) to remove starting materials and major by-products. Cyclisation of the resultant 1-[5-(1-adamantoyloxy)-2-hydroxyphenyl]-3-(1-adamantyl)-1,3-propandione is achieved by treatment with 20 ml of 32% aqueous hydrochloric acid in methanol/dioxane. 6-(1-adamantoyloxy)-2-(1-adamantyl)-4H-chromen-4-one is obtained:

Workup

  1. extractionextracted with ethyl acetate
  2. washThe combined organic layers are washed 3 times with 1 N aqueous hydrochloric acid
  3. dry with materialsubsequently with aqueous sodium carbonate solution, dried over magnesium sulfate
  4. concentrationconcentrated in vacuo
  5. dissolutionThe crude product is dissolved in dry dimethylformamide
  6. additionadded dropwise at 5° to a suspension of 330 mg of sodium hydride (80% in mineral oil) in dry dimethylformamide
  7. customThe cooling bath is removed
  8. stirringthe mixture is stirred for 4 hours at room temperature
  9. additionThen 1.5 ml of acetic acid and 250 ml of water are added
  10. extractionfollowed by extraction with ethyl acetate
  11. dry with materialThe combined extracts are dried over magnesium sulfate
  12. customevaporated in vacuo
  13. customThe residue is chromatographed on silica gel (cyclohexane/ethyl acetate 6/1)
  14. customto remove

Sources & evidence

ORD record
ord-93b6b5434a474444ba8907e8177a6e2e
Source dataset
uspto-grants-2002_02
Patent number
US06346626B1

Reaction notes

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