Dichloroacetic Acid → HCID 12812440, compound

HRID 848197Notes

Reaction equation

HRID 848197 reaction equation
[H-].[Na+].Cl[CH:4](Cl)[C:5]([OH:7])=[O:6].[Cl:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]([CH3:24])([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[OH:17])=[C:12]([OH:25])[CH:11]=1.[OH-].[Na+]>O1CCOCC1>[Cl:9][C:10]1[CH:15]=[CH:14][C:13]2[C:16]([CH3:24])([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[O:17][CH:4]([C:5]([OH:7])=[O:6])[O:25][C:12]=2[CH:11]=1

Participants

6

Reactant 4

HCID 6597Dichloroacetic AcidHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 13076852HCID 13076852, compound

Product 1

HCID 12812440HCID 12812440, compoundYield 109.4%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent3×

Conditions

Temperature
95 °C

Procedure

A mixture of 9.85 g of sodium hydride as a 50% oil suspension, 100 ml of dioxane, 0.73 g of dibenzo-18-courone-6 was stirred and a solution of 11.31 g of dichloroacetic acid in 120 ml of dioxane was added thereto at room temperature with stirring. Then, a solution of 14.550 g of 4-chloro-2-hydroxy-α-methyl-α-phenyl benzene methanol in 200 ml dioxane was added thereto dropwise and the mixture was then refluxed for 6 hours at 95° C. and then returned to room temperature. The reaction mixture was poured into ice and 10 ml of 2 N sodium hydroxide were added thereto. The aqueous phase was washed with 300 ml of ether, was acidified with 20 ml of concentrated hydrochloric acid and then was extracted 3 times with 250 ml of ether. The ether extracts were washed twice with 100 ml of water and the acid of the organic phase was extracted twice with 250 ml of a 5% aqueous solution of sodium bicarbonate. The aqueous phase was washed with 100 ml of ether and was acidified again with 50 ml of concentrated hydrochloric acid. The acid was again extracted 4 times with 250 ml of ether, and the decanted organic phase was washed 3 times with 100 ml of water, dried over magnesium sulfate, treated with activated carbon, filtered and evaporated to dryness under reduced pressure to obtain 19.5 g of 7-chloro-4-methyl-4-phenyl-[4H]-1,3-benzodioxin-2-carboxylic acid (mixture of two racemates of diastereoisomers).

Workup

  1. stirringat room temperature with stirring
  2. customreturned to room temperature
  3. additionwere added
  4. washThe aqueous phase was washed with 300 ml of ether
  5. extractionwas extracted 3 times with 250 ml of ether
  6. washThe ether extracts were washed twice with 100 ml of water
  7. extractionthe acid of the organic phase was extracted twice with 250 ml of a 5% aqueous solution of sodium bicarbonate
  8. washThe aqueous phase was washed with 100 ml of ether
  9. extractionThe acid was again extracted 4 times with 250 ml of ether
  10. washthe decanted organic phase was washed 3 times with 100 ml of water
  11. dry with materialdried over magnesium sulfate
  12. additiontreated with activated carbon
  13. filtrationfiltered
  14. customevaporated to dryness under reduced pressure

Sources & evidence

ORD record
ord-f374b72b94a54b38a4c039f1a80e9f30
Source dataset
uspto-grants-1981_10
Patent number
US04294845

Reaction notes

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