Br[C:2]1[CH:7]=[CH:6][N:5]=[CH:4][CH:3]=1.Cl.CC[O:11][CH2:12][CH3:13].[Mg+2].[Br-].[Br-].C(#N)[C:18]1[C:19](=C[CH:22]=[CH:23][CH:24]=1)[NH2:20].S(=O)(=O)(O)O>C1C=CC=CC=1>[NH2:20][C:19]1[CH:18]=[CH:24][CH:23]=[CH:22][C:13]=1[C:12]([C:2]1[CH:7]=[CH:6][N:5]=[CH:4][CH:3]=1)=[O:11]
4-Bromopyridine (10) (49.38 g, 0.254 mol, free based from the hydrochloride by partitioning between ether and saturated bicarbonate) and diethyl ether (200 mL) was added over 1 h to a cooled solution (−78° C.) of n-butyl lithium (0.381 mol of a 2.5 M solution in hexane) under argon. After 30 min at (−78° C.), magnesium bromide diethyl etherate (98.37 g, 0.381 mol) was added via a dry powder addition funnel. After 1 h at −78° C., the reaction mixture was transferred to a jacketed addition funnel at −50° C., the solution was added to a cooled solution (−50° C.) of anthranilonitrile (15.0 g, 0.127 mol) and benzene (400 mL) over 10 minutes. The reaction was allowed to warm to 23° C. After 16 h, the reaction was poured into 18% sulfuric acid (100 mL), and was digested for 1 h. The resultant mixture was extracted with ethyl acetate ((400 mL), washed with water (3×400 mL), and dried (MgSO4). After concentration in vacuo, the residue was purified by flash chromatography in a step gradient fashion (one liter methylene chloride; one liter ethyl acetate:methylene chloride 1:9; one liter ethyl acetate:methylene chloride 2:8; one liter ethyl acetate:methylene chloride 3:7; one liter ethyl acetate:methylene chloride 4:6) which afforded 4-(2-aminobenzoyl)pyridine (12) as a solid: Mass Spectrum (CI) 199 (MH+).
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