5-BROMO-3-CHLORO-2-FORMYLPYRIDINE

To a solution of 5-bromo-3-chloro-N-methoxy-N-methylpicolinamide (9.0 g, 32.3 mmol, 1 eq) in THF (100 mL), the LAH solution (IM in THF) (16.12 mL, 16.1 mmol, 0.5 eq) was added at -70°C for 15 mm. Reaction was continued at the same temperature for another 2 h. After completion of reaction (monitored by TLC), RM was quenched with sat. Na2SO4 solution and extracted with EtOAc (3x250 mL). The organiclayer was washed with water (500 mL), brine (500 mL), dried over Na2SO4, filtered and the solvent was evaporated under reduced pressure to get the crude product which was purified by flash CC to afford 5- bromo-3-chloropicolinaldehyde (5.0 g, 71percent) as brown gum.DMP (45.83g, 102.lOmmoI) was added portion wise to a stirred solution of (5-bromo-3-chloropyridin-2-yl)-methanol (16g, 72.O7mmoI) in DCM (320mL) at 0°C and stirred for 16h at RT. The RM was filtered through celite and washed with DCM (3x100mL).The filtrate was washed with Aq.NaHCO3 (200mL), water (200mL), brine(250mL), dried (Na2SO4), filtered, concentrated under reduced pressure to give crude. The crude was purified by CC (0-5percent EtOAc in PE) to give 5-bromo-3-chloropicolinaldehyde (lOg, 66percent) as light yellow solid.[01340] A mixture of (5-bromo-3-chloropyridin-2-yl)methanol (2 g, 8.99 mmol, 1.00 equiv), Mn02 (7.77 g, 89.34 mmol, 9.94 equiv), and dichloromethane (150 mL) was stirred for overnight at 40°C. The solids were filtrated out and the filtrate was concentrated. The residue was purified by a silica gel colunm eluting with ethyl acetate/petroleum ether (1/20) to afford the title compound (1.1 g, 56percent) as a light yellow solid. LCMS [M+H] 222.5-Bromo-3-chloropicolylaldehyde 2.06 gAnd 1.00 g of 1-butylamineIn 10 ml of toluene, While performing azeotropic dehydration using a Dean-Stark tube, It was heated to reflux for 2 hours.Then, The solvent was distilled off under reduced pressure, To the residue was added acetic acid 10 mlAnd 1.05 g of nitroethane were added, Followed by stirring at 100 C. for 40 minutes.After completion of the reaction, The reaction mixture was allowed to cool to room temperature, 30 ml of water was added, and the mixture was extracted with ethyl acetate (50 ml × 2).The organic layers were combined, dried over anhydrous sodium sulfate and then saturated brine, dried, The solvent was distilled off under reduced pressure, The residue was purified by silica gel column chromatography eluting with ethyl acetate-hexane (3: 97)0.76 g of the objective compound was obtained as brown crystals.Toluene 10ml solution of 5-bromo-3-chloro-picolylamine aldehyde 2.06g and 1-butylamine 1.00g , with azeotropic dehydration using a Dean Stark tube was 2 hours heating under reflux.Then, the solvent was distilled off under reduced pressure, the residue was added acetic acid 10ml and nitroethane 1.05 g, was stirred for 40 minutes at 100 C..After completion of the reaction, the reaction mixture was extracted (50 ml x 2) with cooling with ethyl acetate adding water 30ml to room temperature.After dehydration and drying in this order brine followed by sodium sulfate anhydride combined organic layers evaporated under reduced pressure, the residue was diluted with ethyl acetate - by silica gel column chromatography eluting with hexane (three ninety-seven) purified to obtain the desired product 0.76g as a brown crystals.

Molecular Weight:220.45
XLogP3:2
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:1
Exact Mass:218.90865
Monoisotopic Mass:218.90865
Topological Polar Surface Area:30
Heavy Atom Count:10
Complexity:133
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes