1-Naphthol → HCID 23035864, compound

HRID 1710206Notes

Reaction equation

HRID 1710206 reaction equation
[CH3:1][O:2][C:3]12[CH2:12][CH:7]3[CH2:8][CH:9]([CH2:11][CH:5]([CH2:6]3)[C:4]1=[CH:13][C:14]1[CH:23]=[CH:22][C:21]3[C:16](=[CH:17][C:18]([O:24]C)=[CH:19][CH:20]=3)[CH:15]=1)[CH2:10]2.C1C=CC2C(=CC=CC=2[OH:36])C=1.[CH2:37]([S-])[CH3:38].[Na+]>CN(C=O)C>[CH3:1][O:2][C:3]12[CH2:12][CH:7]3[CH2:8][CH:9]([CH2:11][CH:5]([CH2:6]3)[C:4]1=[CH:13][C:14]1[CH:23]=[CH:22][C:21]3[C:16](=[CH:17][C:18]([O:24][C:37](=[O:36])[CH3:38])=[CH:19][CH:20]=3)[CH:15]=1)[CH2:10]2

Participants

5

Reactant 3

HCID 70051-Naphthol2×HCID 4459711Sodium ethanethiolateHCID 23035860HCID 23035860, compound

Product 1

HCID 23035864HCID 23035864, compoundYield 25.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

Crude methoxy(7-methoxynaphth-2-yl)methylene adamantane (247 mg, 0.739 mmol) was added to sodium ethylthiolate (62 mg, 0.743 mmol) in dry DMF (4 ml) and the solution was refluxed under argon for 4 hours deprotecting the aromatic methoxy moiety to the naphthol. Excess sodium ethanethiolate (122 mg, 1.45 mmol) was added in two portions during the reflux to push the demethylation to completion. The naphthol was worked up by partitioning the cooled solution between EtOAc and minimal H2O. Traces of naphthol in the aqueous layer were recovered with two EtOAc washes. The EtOAc layers were dried and evaporated. The crude naphthol was immediately acylated upon dissolution in acetic anhydride (1 ml) and pyridine (2 ml) with gentle warming to 50° C. After evaporation, the reaction mixture was chromatographed on a silica gel column prewashed with 10% EtOAc/hexanes containing 1% triethylamine, eluting with the same EtOAc/hexanes/TEA solvent mixture. The four-step reaction sequence--oxidation, enol ether formation, aromatic demethylation and acylation--gave 69.3 mg (25.8%) of methoxy(7-acetoxynaphth-2-yl)methylene adamantane, m.p. 125° C.

Workup

  1. temperaturethe solution was refluxed under argon for 4 hours
  2. temperaturereflux
  3. customby partitioning the cooled solution between EtOAc and minimal H2O
  4. customTraces of naphthol in the aqueous layer were recovered with two EtOAc washes
  5. dry with materialThe EtOAc layers were dried
  6. customevaporated
  7. dissolutionThe crude naphthol was immediately acylated upon dissolution in acetic anhydride (1 ml)
  8. customAfter evaporation
  9. customthe reaction mixture was chromatographed on a silica gel column
  10. washeluting with the same EtOAc/hexanes/TEA solvent mixture
  11. customThe four-step reaction sequence

Sources & evidence

ORD record
ord-fd1cae68bd864903875a7c886f573d31
Source dataset
uspto-grants-1990_08
Patent number
US04952707

Reaction notes

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