2-bromo-3-methoxynaphthalene

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The title compound was synthesized as described above from 2-bromo-3-methoxynaphthalene and ethylene oxide.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A RBF was charged 2-methoxynaphthalene (2.00 g, 12.64 mmol) and THF (30 mL) to give a clear solution. n-butyllithium (2.5M in hexanes) (5.66 mL, 14.16 mmol) was added dropwise. The flask was cooled in a dry ice-acetone bath for 10 min and 1,2-dibromoethane (1.634 mL, 18.96 mmol) was added dropwise. The reaction was warmed to room temperature and stirred for 16 hours. NaOH (1 M, 10 mL, 10 mmol 0 was added and the reaction was heated to reflux for 1 hour. The mixture was cooled to room temperature and extracted with DCM (2×), and the combined organic extracts were dried over magnesium sulfate, filtered, and concentrated. The crude solid was recrystallized from heptane to give 2-bromo-3-methoxynaphthalene (1.75 g, 7.38 mmol, 58.4% yield) as an off-white solid. m/z (ESI) 237.1 (M+H)+. to give a clear solution The flask was cooled in a dry ice-acetone bath for 10 min the reaction was heated to reflux for 1 hour The mixture was cooled to room temperature extracted with DCM (2×) the combined organic extracts were dried over magnesium sulfate filtered concentrated The crude solid was recrystallized from heptane

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A screw cap vial was charged with (E)-ethyl 3-(2-amino-5-(benzylthio)phenyl)acrylate (1.00 g, 3.19 mmol), xantphos (0.092 g, 0.160 mmol), pd2(dba)3 (0.073 g, 0.080 mmol), cesium carbonate (2.079 g, 6.38 mmol) and CPME (6.38 ml). The vial was purged with Argon, sealed and heated to 110° C. for 10 minutes. The reaction was cooled to room temperature and 2-bromo-3-methoxynaphthalene (0.832 g, 3.51 mmol) was added and the reaction was continued heating at 110° C. for an additional 90 min. The mixture was cooled to room temperature, diluted with EtOAc, and filtered through celite with the aid of EtOAc. The filtrate was concentrated. The oily residue was taken up in 2-PrOH (it did not dissolve and remained an oil). The mixture was then concentrated to give a yellow solid with some oily solid present. The mixture was taken up in 2-PrOH to give a suspension, and the suspension was stirred overnight, which broke up the darker, oily solid. The mixture was then filtered, and the filtered solid was washed with 2-PrOH (3×). The collected solid was dried on the filter under a flow of N2 (g) for 15 min to give (E)-ethyl 3-(5-(benzylthio)-2-((3-methoxynaphthalen-2-yl)amino)phenyl)acrylate (1.35 g, 2.87 mmol, 90% yield). m/z (ESI) 470.1 A screw cap vial The vial was purged with Argon sealed The reaction was cooled to room temperature the reaction was continued heating at 110° C. for an additional 90 min The mixture was cooled to room temperature filtered through celite with the aid of EtOAc The filtrate was concentrated did not dissolve The mixture was then concentrated to give a yellow solid with some oily solid present to give a suspension The mixture was then filtered the filtered solid was washed with 2-PrOH (3×) The collected solid was dried on the filter under a flow of N2 (g) for 15 min

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The title compound was synthesized as described above from 2-bromo-3-methoxynaphthalene and ethylene oxide.