Anthranilic Acid → 3-Chloro-1-methylnaphthalene

HRID 1635947Notes

Reaction equation

HRID 1635947 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([CH3:8])O[C:4](=O)[CH:3]=1.O[C:11]1[CH:16]=[C:15](C)O[C:13](=O)[CH:12]=1.P(Cl)(Cl)(Cl)=O.FC(F)(F)C(O)=O.C(ON=O)CC(C)C.C(O)(=O)C1C(=CC=CC=1)N>COCCOC.CCCCCC.C(OC(=O)C)C>[Cl:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:13]2[C:4]([CH:3]=1)=[CH:15][CH:16]=[CH:11][CH:12]=2

Participants

9

Reactant 6

HCID 227Anthranilic Acid2×HCID 6422Trifluoroacetic acidHCID 8053Isoamyl Nitrite2×HCID 24813Phosphorus oxychlorideHCID 5391414-Chloro-6-methyl-2H-pyran-2-oneHCID 546757574-Hydroxy-6-methyl-2-pyrone

Product 1

HCID 186736453-Chloro-1-methylnaphthaleneYield 55%

Reagents, catalysts & solvents 2

HCID 80711,2-DimethoxyethaneSolvent2×HCID 21226206Ethyl acetate hexaneSolvent

Procedure

A three-neck round-bottomed flask was equipped with a reflux condenser and two addition funnels. Dry DME(200 ml) was introduced into the flask and 4-chloro-6-methyl-2-pyrone(3.24 g, 22.4 mmol) prepared according to the procedure described in a literature (see: M. J. D. Van Dam et F. KOGL, Recueil 83, 39, 1964) from 4-hydroxy-6-methyl-2-pyrone and phosphorusoxychloride, and trifluoroacetic acid(0.1 ml) were added thereto. Isoamylnitrite(3.15 g, 26.9 mmol) and anthranilic acid(3.69 g, 26.9 mmol) each dissolved in DME(50 ml) were introduced into the respective funnels. The isoamylnitrite solution and anthranilic acid solution were added dropwise simultaneously while keeping the reflux condition. After confirming that the starting materials were completely used, addition was stopped and the reaction solution was cooled. The solvent was removed under reduced pressure and the residue was dissolved in methyene chloride(100 ml) and the organic layer was sequentially washed with 5% aqueous hydrochloric acid solution, 5% aqueous sodium hydroxide solution and water. The organic layer was dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to column chromatography(eluent: n-hexane/ethylacetate=9/1, v/v) to give 2.60 g(14.7 mmol, Yield 55%) of the title compound.

Workup

  1. customA three-neck round-bottomed flask was equipped with a reflux condenser
  2. additiontwo addition funnels
  3. customprepared
  4. additionwere added
  5. additionwere introduced into the respective funnels
  6. additionaddition
  7. temperaturethe reaction solution was cooled
  8. customThe solvent was removed under reduced pressure
  9. dissolutionthe residue was dissolved in methyene chloride(100 ml)
  10. washthe organic layer was sequentially washed with 5% aqueous hydrochloric acid solution, 5% aqueous sodium hydroxide solution and water
  11. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-0d08edad138746408d90143f616efb8e
Source dataset
uspto-grants-2003_01
Patent number
US06511978B1

Reaction notes

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