Potassium Carbonate → HCID 18992016, compound

HRID 375722Notes

Reaction equation

HRID 375722 reaction equation
[OH:1][C:2]1[C:3]([CH3:13])=[C:4]([C:8]([CH3:12])=[C:9]([OH:11])[CH:10]=1)[C:5]([OH:7])=[O:6].[N+:14]([C:17]1[CH:24]=[CH:23][C:20]([CH2:21]Br)=[CH:19][CH:18]=1)([O-:16])=[O:15].C(=O)([O-])[O-].[K+].[K+]>C(OC)(C)(C)C>[OH:1][C:2]1[C:3]([CH3:13])=[C:4]([C:8]([CH3:12])=[C:9]([OH:11])[CH:10]=1)[C:5]([O:7][CH2:21][C:20]1[CH:23]=[CH:24][C:17]([N+:14]([O-:16])=[O:15])=[CH:18][CH:19]=1)=[O:6]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 660114-Nitrobenzyl bromideHCID 11789846HCID 11789846, compound

Product 1

HCID 18992016HCID 18992016, compoundYield 62.3%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Procedure

To a solution of 91.1 g of 3,5-dihydroxy-2,6 -dimethylbenzoic acid and 108.0 g of p-nitrobenzyl bromide were added 165.9 g of potassium carbonate. The mixture was heated at reflux under stirring for 4 hours. After cooling to room temperature, the mixture was filtered, and the unsoluble material was washed with 0.5 l of ethyl acetate. The filtrate was diluted with 0.5 l of ethyl acetate and washed with ice-cold 3N hydrochloric acid and with brine. The organic layer was dried over sodium sulfate and evaporated in vacuo. To the remaining, crystallizing oil were added 0.6 1 of tert-butylmethylether, and the suspension was stirred for 1 hour. Unsoluble material was filtered off and the filtrate was evaporated in vacuo. The remaining oil was dissolved in 300 ml of methylene chloride. Upon crystallization, 200 ml of hexane were added and the crystals isolated by filtration. This material was suspended once more in 400 ml of tert-butylmethylether and the unsoluble material was removed by filtration. Evaporation of the filtrate in vacuo and crystallization of the residue from methylene chloride/hexane afforded 98.8 g of p-nitrobenzyl 3,5-dihydroxy-2,6-dimethylbenzoate as yellow crystals of m.p. 164°-166° C.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux
  3. filtrationthe mixture was filtered
  4. washthe unsoluble material was washed with 0.5 l of ethyl acetate
  5. additionThe filtrate was diluted with 0.5 l of ethyl acetate
  6. washwashed with ice-cold 3N hydrochloric acid and with brine
  7. dry with materialThe organic layer was dried over sodium sulfate
  8. customevaporated in vacuo
  9. customTo the remaining, crystallizing oil
  10. additionwere added 0.6 1 of tert-butylmethylether
  11. stirringthe suspension was stirred for 1 hour
  12. filtrationUnsoluble material was filtered off
  13. customthe filtrate was evaporated in vacuo
  14. dissolutionThe remaining oil was dissolved in 300 ml of methylene chloride
  15. customUpon crystallization, 200 ml of hexane
  16. additionwere added
  17. customthe crystals isolated by filtration
  18. customthe unsoluble material was removed by filtration
  19. customEvaporation of the filtrate
  20. customin vacuo and crystallization of the residue from methylene chloride/hexane

Sources & evidence

ORD record
ord-bcac59d9b3d548fc88cc23b4e58d275f
Source dataset
uspto-grants-1996_01
Patent number
US05486466

Reaction notes

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