Pyridine → 1-Naphthalenecarboxylic acid, 6-methoxy-5-(trifluoromethyl)-, methyl ester

HRID 1904090Notes

Reaction equation

HRID 1904090 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:14]2[C:9](=[C:10](I)[C:11]([O:15][CH3:16])=[CH:12][CH:13]=2)[CH:8]=[CH:7][CH:6]=1)=[O:4].[F:18][C:19](I)([F:21])[F:20].N1C=CC=CC=1>C(OCC)C.C(OCC)(=O)C.[Cu]>[CH3:1][O:2][C:3]([C:5]1[C:14]2[C:9](=[C:10]([C:19]([F:21])([F:20])[F:18])[C:11]([O:15][CH3:16])=[CH:12][CH:13]=2)[CH:8]=[CH:7][CH:6]=1)=[O:4]

Participants

6

Reactant 3

HCID 1049PyridineHCID 16843TrifluoroiodomethaneHCID 13672312Methyl 5-iodo-6-methoxynaphthalene-1-carboxylate

Product 1

HCID 136041041-Naphthalenecarboxylic acid, 6-methoxy-5-(trifluoromethyl)-, methyl esterYield 75.1%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 21584169Diethylether ethylacetateSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 5-iodo-6-methoxy-1-naphthalenecarboxylic acid methyl ester (10.26 g, 30 mmoles, described in Example 1f), trifluoromethyl iodide (12 g, 61.2 mmoles), freshly prepared copper powder (5.7 g, prepared according to the procedure of R. Q. Brewster and T. Groening, "Organic Syntheses", Coll. Vol. II, John Wiley and Sons, New York, N.Y., U.S.A., 1948, p. 445) and pyridine (45 ml) was charged into a stainless steel autoclave. The vessel was shaken and heated at 120° C. for 20 hr and cooled to room temperature. The mixture was diluted with diethyl ether-ethyl acetate (1:1). The insoluble material was removed by filtration. The filtrate was washed with 1 N aqueous HCl, water and dried (MgSO4). The solvent was removed under reduced pressure. The residue was crystallized from ethanol to give 6.4 g of 5-(trifluoromethyl)-6-methoxy-1-naphthalenecarboxylic acid methyl ester; mp 79°-80° C., NMR (CDCl3) δ3.95 (s, 6H), 8.00 (m, 5H). A mixture of the latter ester (6.3 g, 22 mmoles), 1 N aqueous NaOH solution (34.12 ml) and methanol (100 ml) was stirred at 20°-22° C. for 4 hr. The mixture was adjusted to pH 7 with 1 N aqueous HCl, methanol was removed from the mixture by distillation and the concentrated mixture was made acidic (pH 2) with 1 N aqueous HCl. The resulting precipitate was collected and dried to yield 6 g of the title compound; mp 218°-219° C.; NMR (DMSO-d6) δ4.0 (s, 3H),8.3 (m, 5H), 10.6 (broad, 1H).

Workup

  1. customprepared
  2. temperaturecooled to room temperature
  3. customThe insoluble material was removed by filtration
  4. washThe filtrate was washed with 1 N aqueous HCl, water
  5. dry with materialdried (MgSO4)
  6. customThe solvent was removed under reduced pressure
  7. customThe residue was crystallized from ethanol

Sources & evidence

ORD record
ord-bf33e2806ed14eafb5d98dc3af50ff4d
Source dataset
uspto-grants-1984_03
Patent number
US04439617

Reaction notes

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