Sulfuric Acid → 3-Chloro-6-hydroxy-2-methoxybenzaldehyde

HRID 485165Notes

Reaction equation

HRID 485165 reaction equation
COC[O:4][C:5]1[CH:10]=[CH:9][C:8]([Cl:11])=[C:7]([O:12][CH3:13])[CH:6]=1.C1([Li])C=CC=CC=1.CN(C)[CH:23]=[O:24].S(=O)(=O)(O)O>CCOCC>[Cl:11][C:8]1[C:7]([O:12][CH3:13])=[C:6]([C:5]([OH:4])=[CH:10][CH:9]=1)[CH:23]=[O:24]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 6228DimethylformamideHCID 130921141-Chloro-2-methoxy-4-(methoxymethoxy)benzeneHCID 178506676HCID 178506676, compound

Product 1

HCID 202715353-Chloro-6-hydroxy-2-methoxybenzaldehyde

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

4-Chloro-3-methoxyphenol methoxymethyl ether (3.1 g, 0.0153 M) in dry ether (3.5 ml) was added dropwise to a solution of phenyllithium (from 0.21 g lithium and 2.4 g bromobanzene) in dry ether (12 ml) under nitrogen and the mixture stirred at room temperature (3 days). A solution of dry dimethylformamide (1.12 g, 0.0153 M) in dry ether (1 ml) was then added dropwise over 15 mins and the mixture stirred at room temperature (1 hr). The reaction mixture was poured into 2 N sulphuric acid (100 ml) and extracted with ethyl acetate. The combined extracts were dried (sodium sulphate) and evaporated. The residue was dissolved in methanol (25 ml), 3 N hydrochloric acid (10 ml) added and the resultant solution stirred at 65° C. for 30 mins. The solvent was removed in vacuo and the residue diluted with water (50 ml) and extracted with ether. The combined extracts were dried (sodium sulphate) and evaporated. The residue was chromatographed on silica (MFC) eluting with chloroform. The fractions were combined and evaporated to give 3-chloro-6-hydroxy-2-methoxybenzaldehyde as an oil which crystallised on standing. (Found: m/e 186.0084. C8H7ClO3 requires M185.0082).

Workup

  1. stirringthe mixture stirred at room temperature (1 hr)
  2. extractionextracted with ethyl acetate
  3. dry with materialThe combined extracts were dried (sodium sulphate)
  4. customevaporated
  5. dissolutionThe residue was dissolved in methanol (25 ml)
  6. addition3 N hydrochloric acid (10 ml) added
  7. stirringthe resultant solution stirred at 65° C. for 30 mins
  8. customThe solvent was removed in vacuo
  9. additionthe residue diluted with water (50 ml)
  10. extractionextracted with ether
  11. dry with materialThe combined extracts were dried (sodium sulphate)
  12. customevaporated
  13. customThe residue was chromatographed on silica (MFC)
  14. washeluting with chloroform
  15. customevaporated

Sources & evidence

ORD record
ord-bc0fb9a29db44f508df5a57734f7e72c
Source dataset
uspto-grants-1985_08
Patent number
US04535183

Reaction notes

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