Water → HCID 12812427, compound

HRID 848193Notes

Reaction equation

HRID 848193 reaction equation
Cl[CH:2](Cl)[C:3]([OH:5])=[O:4].[H-].[Na+].[Cl:9][C:10]1[CH:11]=[CH:12][C:13](C(C)(C)C)([OH:24])[CH:14]([CH:16]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[OH:17])[CH:15]=1.O>O1CCOCC1>[Cl:9][C:10]1[CH:11]=[CH:12][C:13]2[O:24][CH:2]([C:3]([OH:5])=[O:4])[O:17][C:16]([C:14]([CH3:16])([CH3:15])[CH3:13])([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C:14]=2[CH:15]=1

Participants

6

Reactant 4

HCID 962WaterHCID 6597Dichloroacetic AcidHCID 24758Sodium hydrideHCID 86738038HCID 86738038, compound

Product 1

HCID 12812427HCID 12812427, compound

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent3×

Conditions

Temperature
80 °C

Procedure

A solution of 5.82 ml of dichloroacetic acid in 100 ml of dioxane was added dropwise with stirring to a mixture of 12.8 g of sodium hydride in a 50% oil suspension, 100 ml of anhydrous dioxane and 600 mg of dibenzo-18-couronne-6 kept at room temperature and a solution of 14.1 g of 5-chloro-2-tert.-butyl-2-hydroxy-α-phenyl-benzene-methanol in 100 ml of dioxane was added dropwise at room temperature. The mixture was heated at 80° C. for 6 hours and was then cooled to room temperature which was kept on an ice bath. 400 ml of water were added and the aqueous phase was extracted with 600 ml of ether. The ether extract was extracted 3 times with 100 ml of 0.1 N sodium hydroxide solution and the aqueous phase was acidified with 2 N hydrochloric acid and was extracted 3 times with 150 ml of ether. The organic extracts were washed 3 times with 100 ml of water and were extracted with a saturated sodium bicarbonate solution and then 3 times with 100 ml of water. The combined aqueous phases were washed 3 times with ether and was acidified with 2 N hydrochloric acid. The aqueous phase was extracted 4 times with 150 ml of ether and the ether phases were washed 3 times with water, dried over magnesium sulfate, treated with activated carbon and evaporated to dryness to obtain 9.1 g of raw 6-chloro-4-tert.-butyl-4-phenyl-[4H]-1,3-benzodioxin-2-carboxylic acid (mixture of two racemates diastereoisomers).

Workup

  1. customkept at room temperature
  2. temperaturewas then cooled to room temperature which
  3. customwas kept on an ice bath
  4. extractionthe aqueous phase was extracted with 600 ml of ether
  5. extractionThe ether extract
  6. extractionwas extracted 3 times with 100 ml of 0.1 N sodium hydroxide solution
  7. extractionwas extracted 3 times with 150 ml of ether
  8. washThe organic extracts were washed 3 times with 100 ml of water
  9. extractionwere extracted with a saturated sodium bicarbonate solution
  10. washThe combined aqueous phases were washed 3 times with ether
  11. extractionThe aqueous phase was extracted 4 times with 150 ml of ether
  12. washthe ether phases were washed 3 times with water
  13. dry with materialdried over magnesium sulfate
  14. additiontreated with activated carbon
  15. customevaporated to dryness

Sources & evidence

ORD record
ord-c8ab4b4746f54c619a1c854cf9892e6d
Source dataset
uspto-grants-1981_10
Patent number
US04294845

Reaction notes

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