7-Bromo-2-methylquinoline

yellow powder

Doebner Miller synthesis: 3-Bromoaniline (10 mL, 92 mmol) was added to a solution of 37 percent HCl at 0 °C (200 mL). Paraldehyde (11 mL, 0.8 mol, 9 eq) was then introduced and the mixture was left to react at room temperature for 1 hour, and then heated to reflux temperature for 3 hours. After cooling to 0 °C, a saturated aquous solution of sodium hydroxide (200 mL) was slowly added and the mixture was extracted with dichloromethane. The organic layer was washed with water and brine, then dried over MgSO1) Preparation of 7-bromo-2-methyl-quinolineDoebner-Miller synthesis:3-bromoaniline (3 mL, 27 mmol), was added to a solution of 37percent HC1 at 0°C (24 mL). Paraldehyde (8 mL, 83 mmol, 3 eq) was then introduced and the mixture was left to react at room temperature for 1 hour, then refluxed for 3 hours. After cooling to 0°C, sodium hydroxide (25 mL) was added dropwise and the mixture was extracted with dichloromethane. The organic layer was washed twice with water and brine, then dried over MgS03-Bromoaniline (10 mL, 92 mmol) was added to a solution of 37 percent HC1 at 0 °C (200 mL). Paraldehyde (1 1 mL, 0.8 mol, 9 eq) was then introduced and the mixture was left to react at room temperature for 1 hour, and then heated to reflux temperature for 3 hours. After cooling to 0 °C, a saturated aquous solution of sodium hydroxide (200 mL) was slowly added and the mixture was extracted with dichloromethane. The organic layer was washed with water and brine, then dried over MgS0Doebner Miller synthesis: 3-Bromoaniline (10 mL, 92 mmol) was added to a solution of 37 % HCl at 0 C (200 mL). Paraldehyde (11 mL, 0.8 mol, 9 eq) was then introduced and the mixture was left to react at room temperature for 1 hour, and then heated to reflux temperature for 3 hours. After cooling to 0 C, a saturated aquous solution of sodium hydroxide (200 mL) was slowly added and the mixture was extracted with dichloromethane. The organic layer was washed with water and brine, then dried over MgSO4, and concentrated under reduced pressure. The crude product was obtained as a mixture of 5-bromoquinaldine and 7-bromoquinaldine that were separated by column chromatography (SiO2, cyclohexane-AcOEt 9:1). The 7-bromoquinaldine regioisomer was obtained as a sand yellow solid (9, 3 g, 46 %). Molecular formula: C10H8BrN. Molecular weight: 222.08 g.mol-1. IR (film): 1610, 1494, 1264, 841, 736 cm-1. Tfusion: 57 C. 1H NMR: delta 8.09 (s, 1H, H8), 7.80 (d, J = 8.2 Hz, 1H, H4), 7.39 (m, 2H, H5 et H7), 7.12 (d, J = 8.2 Hz, 1H, H3), 2.61 (s, 3H, H9). 13C NMR: delta 160.3 (s, C2), 148.6 (s, C8a), 136.2 (s, C4), 131.2 (s, C8), 129.4 (s, C5), 128.9 (s, C6), 125.3 (s, C4a), 123.7 (s, C7), 122.6 (s, C3), 25.7 (s, C9).General procedure: 2-Methylazaarenes (0.5mmol), iodine (0.375mmol, 95.3mg), CuSO4·5H2O (0.2mmol, 50mg) and CH3CN (2mL) were stirred at 70C for 3h. Then, the reaction mixture was diluted by water and extracted with CH2Cl2 (3×15mL). The residue I2 in organic phase was quenched by Na2S2O3. The combined organic layers were washed with saturated NH4Cl aqueous solution and dried over anhydrous Na2SO4. After filtration, the solvent was evaporated in vacuo. The desired product was obtained by silica gel chromatography (petroleum ether/ethyl acetate, v/v=10/1).

Molecular Weight:222.08
XLogP3:3.3
Hydrogen Bond Acceptor Count:1
Exact Mass:220.98401
Monoisotopic Mass:220.98401
Topological Polar Surface Area:12.9
Heavy Atom Count:12
Complexity:160
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes