1-Naphthylamine → (3-Chloro-quinoxalin-2-yl)-naphthalen-1-yl-amine

HRID 44206

Reaction equation

HRID 44206 reaction equation
C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.Cl[C:48]1[C:57]([Cl:58])=[N:56][C:55]2[C:50](=[CH:51][CH:52]=[CH:53][CH:54]=2)[N:49]=1.[C:59]1([NH2:69])[C:68]2[C:63](=[CH:64][CH:65]=[CH:66][CH:67]=2)[CH:62]=[CH:61][CH:60]=1.CC(C)([O-])C.[K+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Cl:58][C:57]1[C:48]([NH:69][C:59]2[C:68]3[C:63](=[CH:64][CH:65]=[CH:66][CH:67]=3)[CH:62]=[CH:61][CH:60]=2)=[N:49][C:50]2[C:55]([N:56]=1)=[CH:54][CH:53]=[CH:52][CH:51]=2

Participants

6

Reactant 4

HCID 86401-NaphthylamineHCID 166592,3-DichloroquinoxalineHCID 634876Binap, (A+-)-HCID 23665647Potassium tert-butoxide

Product 1

HCID 86656203(3-Chloro-quinoxalin-2-yl)-naphthalen-1-yl-amineYield 33%

Reagents, catalysts & solvents 1

HCID 167845palladium(II) acetateCatalyst

Procedure

BINAP (93.3 mg, 0.15 mmol) and palladium acetate (22.6 mg, 0.1 mmol) were dissolved in dry xylenes (50 mL) and stirred for 10 min in an inert atmosphere of nitrogen. 2,3-Dichloroquinoxaline (1.99 g, 10 mmol), 1-naphthylamine (1.50 g, 10.5 mmol) and potassium tert-butoxide (1.34 g, 12 mmol) were the added to the reaction mixture which was heated for 22 h under reflux. After cooling to room-temperature, the reaction mixture was filtered and inorganic precipitate washed with dichloromethane (3×50 mL). Removal of the solvent in vacuo results in a residue which was purified using silica gel chromatography (hexanes/EtOAc 9:1). Compound 2c was isolated as yellow-orange crystals, mp=157-159° C. Yield 33%. TLC Rf=0.45 (hexanes/EtOAc 3:1). HPLC/MS: [M+H]+ m/z 306. 1H NMR (CDCl3, 600 MHz): δ 7.50 (td, J=7.2 Hz, 1.2 Hz, 1H), 7.56-7.63 (m, 4H), 7.74 (d, J=8.4 Hz, 1H), 7.78 (dd, J=8.4 Hz, 1.2 Hz, 1H), 7.89 (dd, J=8.4 Hz, 1.2 Hz, 1H), 7.90 (d, J=8.4 Hz, 1H), 7.99-8.04 (m, 2H), 8.54 (d, J=7.2 Hz, 1H). 13C NMR (CDCl3, 150 MHz): δ 118.62, 120.31, 125.01, 125.85, 126.10, 126.26, 126.45, 126.74, 126.79, 127.89, 129.01, 130.42, 133.25, 134.26, 137.25, 138.12, 140.59, 145.71. HRMS: Calcd. for C18H13ClN3 [M+H]+ m/z 306.0793, Observed 306.0786.

Workup

  1. additionadded to the reaction mixture which
  2. temperaturewas heated for 22 h
  3. temperatureunder reflux
  4. temperatureAfter cooling to room-temperature
  5. filtrationthe reaction mixture was filtered
  6. washinorganic precipitate washed with dichloromethane (3×50 mL)
  7. customRemoval of the solvent in vacuo
  8. customresults in a residue which
  9. customwas purified

Sources & evidence

ORD record
ord-a86ac29fa6964ebaa109712e06510298
Source dataset
uspto-grants-2013_09
Patent number
US08541415B2

Linked notes

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