Dimethylformamide → HCID 20271540, compound

HRID 485155Notes

Reaction equation

HRID 485155 reaction equation
BrC1C=CC=CC=1.[Li].O1CCCCC1[O:15][C:16]1[CH:21]=[CH:20][C:19]([O:22][CH2:23][CH2:24][CH3:25])=[C:18]([O:26][CH3:27])[CH:17]=1.CN(C)[CH:30]=[O:31]>CCOCC>[OH:15][C:16]1[C:17]([CH:30]=[O:31])=[C:18]([O:26][CH3:27])[C:19]([O:22][CH2:23][CH2:24][CH3:25])=[CH:20][CH:21]=1

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 7961Bromobenzene2×HCID 3028194LithiumHCID 20271534HCID 20271534, compound

Product 1

HCID 20271540HCID 20271540, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

1 ml of bromobenzene (11.88 ml) was added to a mixture of lithium chips (1.63 g) and anhydrous ether (90 ml) under nitrogen. When the reaction had commenced the remainder of the bromobenzene was added dropwise to the stirred mixture at such a rate as to cause gentle refluxing. After the addition was complete the mixture was stirred and refluxed (1 hr) and then cooled to room temperature. 3-Methoxy-4-n-propoxyphenol tetrahydropyranyl ether (30.03 g, 0.113 M) was added dropwise to the stirred mixture and then stirred at room temperature (3 days). A solution of anhydrous dimethyl formamide (8.5 ml) in anhydrous ether (8.5 ml) was added dropwise to the stirred mixture at such a rate as to cause gentle refluxing, and then stirred for an extra hour. The reaction mixture was poured into 2 N sulphuric acid/ice (200 ml) and extracted with ethyl acetate. The combined extracts were washed with water, dried (sodium sulphate) and evaporated. The residue was dissolved in 95% ethanol (175 ml) and 2 N hydrochloric acid (210 ml) was added. After stirring at room temperature (2 hr) the mixture was diluted with water (500 ml) and extracted with ethyl acetate/ether (1:1). The combined extracts were extracted with 2 N sodium hydroxide solution, the combined aqueous phases acidified with concentrated hydrochloric acid and extracted with ethyl acetate. The combined extracts were washed with water, dried (sodium sulphate) and evaporated. The residue was chromatographed on silica (MFC) eluting with chloroform-methanol (98:2) to give 6-hydroxy-2-methoxy-3-n-propoxybenzaldahyde as an oil.

Workup

  1. additionwas added dropwise to the stirred mixture at such a rate as
  2. additionAfter the addition
  3. temperaturerefluxed (1 hr)
  4. stirringstirred at room temperature (3 days)
  5. stirringstirred for an extra hour
  6. extractionextracted with ethyl acetate
  7. washThe combined extracts were washed with water
  8. dry with materialdried (sodium sulphate)
  9. customevaporated
  10. dissolutionThe residue was dissolved in 95% ethanol (175 ml)
  11. addition2 N hydrochloric acid (210 ml) was added
  12. stirringAfter stirring at room temperature (2 hr) the mixture
  13. additionwas diluted with water (500 ml)
  14. extractionextracted with ethyl acetate/ether (1:1)
  15. extractionThe combined extracts were extracted with 2 N sodium hydroxide solution
  16. extractionextracted with ethyl acetate
  17. washThe combined extracts were washed with water
  18. dry with materialdried (sodium sulphate)
  19. customevaporated
  20. customThe residue was chromatographed on silica (MFC)
  21. washeluting with chloroform-methanol (98:2)
  22. customto give 6-hydroxy-2-methoxy-3-n-propoxybenzaldahyde as an oil

Sources & evidence

ORD record
ord-0197ea407f724364b3ab30844026e3d1
Source dataset
uspto-grants-1985_08
Patent number
US04535183

Reaction notes

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