Sulfuric Acid → Allyl 3-(1-adamantyl)-2-fluoro-4hydroxybenzoate

HRID 2051085Notes

Reaction equation

HRID 2051085 reaction equation
[C:1]12(O)[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.S(=O)(=O)(O)O.C(OC(=O)C)(=O)C.[F:24][C:25]1[CH:36]=[C:35]([OH:37])[CH:34]=[CH:33][C:26]=1[C:27]([O:29][CH2:30][CH:31]=[CH2:32])=[O:28]>ClCCl.CCCCCCC>[C:1]12([C:36]3[C:25]([F:24])=[C:26]([CH:33]=[CH:34][C:35]=3[OH:37])[C:27]([O:29][CH2:30][CH:31]=[CH2:32])=[O:28])[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2

Participants

7

Reactant 4

HCID 1118Sulfuric Acid2×HCID 7918Acetic AnhydrideHCID 641521-AdamantanolHCID 14852522Allyl 2-fluoro-4-hydroxybenzoate

Product 1

HCID 19834509Allyl 3-(1-adamantyl)-2-fluoro-4hydroxybenzoateYield 58.5%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8900HeptaneSolvent

Procedure

In a 250 ml three-necked flask, under nitrogen, one introduces 3.04 g 1-adamantanol, 10 ml of n-heptane and 63 μl concentrated sulfuric acid. Dropwise, 2.16 ml of acetic anhydride are added and stirring is conducted for 3 hours at room temperature. Dropwise, 540 μl concentrated sulfuric acid are added and one adds portionwise 3.92 g of allyl 2-fluoro-4-hydroxybenzoate. After this addition, one adds 25 ml of dichloromethane and agitates at room temperature for 24 hours. After vacuum drying, the solid is taken up in water, neutralized to pH 7 with sodium bicarbonate and extracted with ethyl ether. The organic layer is washed with water and then with a concentrated aqueous sodium chloride solution. After drying over magnesium sulfate, one filters and evaporates the filtrate to obtain 7 g of crude product which is chromatographed on a silica column and eluted with dichloromethane. After trituration with hexane, filtration and drying in an oven at 50° C. there were obtained 3.86 g of the desired product, melting at 219°-222° C.

Workup

  1. additionAfter this addition, one
  2. customAfter vacuum drying
  3. extractionextracted with ethyl ether
  4. washThe organic layer is washed with water
  5. dry with materialAfter drying over magnesium sulfate, one filters
  6. customevaporates the filtrate
  7. customto obtain 7 g of crude product which
  8. customis chromatographed on a silica column
  9. washeluted with dichloromethane
  10. filtrationAfter trituration with hexane, filtration
  11. customdrying in an oven at 50° C.

Sources & evidence

ORD record
ord-8868e71a7e27415d9c1912356378a345
Source dataset
uspto-grants-1991_05
Patent number
US05015758

Reaction notes

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