Hydrochloric Acid → Methyl 6-aminonaphthalene-1-carboxylate

HRID 1925346Notes

Reaction equation

HRID 1925346 reaction equation
FC(F)(F)S(O[C:7]1[CH:16]=C[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:8]=1C([O-])=O)(=O)=O.C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2)CCCCC1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].C(=[NH:68])(C1C=CC=CC=1)C1C=CC=CC=1.Cl.[OH-].[Na+].C[CH2:73][O:74][C:75]([CH3:77])=[O:76]>C(COC)OC.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:73][O:74][C:75]([C:77]1[C:14]2[C:9](=[CH:10][C:11]([NH2:68])=[CH:12][CH:13]=2)[CH:8]=[CH:7][CH:16]=1)=[O:76]

Participants

10

Reactant 7

HCID 313Hydrochloric AcidHCID 8857Ethyl AcetateHCID 14798Sodium HydroxideHCID 62657Potassium Phosphate, TribasicHCID 136809Benzophenone imineHCID 27342162-(Dicyclohexylphosphino)biphenylHCID 86608623HCID 86608623, compound

Product 1

HCID 24823732Methyl 6-aminonaphthalene-1-carboxylate

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of methyl-6-(trifluoromethylsulfonyloxy-1-napthoate (2.0 g, 6.0 mmol) in dimethoxyethane (10 mL) was added Pd2(dba)3 (55 mg, 0.06 mmol), 2-(dicyclohexylphosphino)biphenyl (84 mg, 0.23 mmol), K3PO4 (1.9 g, 8.9 mmol) and benzophenone imine (1.25 mL, 7.5 mmol). The mixture was heated at 90° C. for 10 h. After cooling to ambient temperature, 2N HCl (4 mL) was added the mixture was stirred vigorously for 1 h. EtOAc (5 mL) was added to the reaction and the mixture was basified to pH 14 with 6N NaOH. The aqueous layer was extracted with EtOAc (3×30 mL). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo. The resulting brown residue was purified by silica gel column chromatography (0-25% EtOAc in hexanes) to give the title compound as a orange oil. MS (ESI, pos. ion) m/z: 202.1 (M+1). Mass Calc'd for C12H11NO2: 201.22.

Workup

  1. temperatureAfter cooling to ambient temperature
  2. extractionThe aqueous layer was extracted with EtOAc (3×30 mL)
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated in vacuo
  6. customThe resulting brown residue was purified by silica gel column chromatography (0-25% EtOAc in hexanes)

Sources & evidence

ORD record
ord-7c5c70d2431c429ab684e8e3887f16b1
Source dataset
uspto-grants-2012_05
Patent number
US08178557B2

Reaction notes

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