6-bromo-7-fluoro-3,4-dihydro-1H-quinolin-2-one

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

Procedure: In analogy to the procedure described for the preparation of intermediates A-1 [A], 6-bromo-7-fluoro-3,4-dihydro-1H-quinolin-2-one was reacted with methyl iodide in presence of potassium tert-butoxide to give the title compound as a white foam. MS: 258.0, 259.9 (M+H+).

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 6-bromo-7-fluoro-3,4-dihydroquinolin-2(1H)-one (122-3; 3 g, 0.0012 mol) in N,N-dimethylformamide (30 mL) was added N-chlorosuccinimide in N,N-dimethylformamide (3 mL) (1.4 g, 0.0105 mol) at 70° C. drop wise over a period of 2 h. Reaction mass was allowed to stir at 70° C. for 14 h. The reaction mixture was cooled and diluted with ice cold water. The precipitated solid was filtered and dried to obtain title compound. MS (M−1): 278.12. Reaction mass The reaction mixture was cooled diluted with ice cold water The precipitated solid was filtered dried

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 6-bromo-7-fluoro-3,4-dihydroquinolin-2(1H)-one (122-3; 13 g, 0.02 mol) in toluene (50 mL) was added Lawesson's reagent (21.54 g, 0.0532 mol). Reaction mass was refluxed at 100° C. for 12 h. The reaction mixture was concentrated and directly purified by silica gel column chromatography to obtain title compound. MS (M+1): 261.88. Reaction mass The reaction mixture was concentrated directly purified by silica gel column chromatography

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

Procedure: To a stirred solution of 7-fluoro-3,4-dihydroquinolin-2(1H)-one (122-2; 15 g, 0.090 mol) in N,N-dimethylformamide (50 mL) was added N-bromosuccinimide (19.22 g, 0.108 mol) portion wise at 0° C. Reaction mixture was allowed to stir at room temperature for 12 h. The reaction mixture was concentrated and diluted with ice cold water (150 mL) with constant stirring and the solid residue was filtered and dried to obtain the title compound. 1H NMR (400 MHz, CDCl3) δ 8.0 (bs, 1H), 7.34-7.32 (d, J=7.2 Hz, 1H), 6.59-6.57 (d, J=8.8 Hz, 1H), 2.95-2.91 (t, J=7.6 Hz, 2H), 2.65-2.61 (t, J=−7.6 Hz, 2H). MS (M+1): 245.9. Reaction mixture The reaction mixture was concentrated diluted with ice cold water (150 mL) with constant stirring the solid residue was filtered dried