2-BROMO-6-METHYLANILINE

A mixture of tellurium (21.6 g, 169.4 mmol) and NaBH4 (15.0 g, 396 mmol) in 575 mL of absolute EtOH was heated at reflux under an atmosphere of N2 for 1 hr, then allowed to cool to rt. A solution of 3-bromo-2-nitrotoluene (1c; 7.32 g, 33.8 mmol) in 25 mL EtOH was added all at once and the mixture stirred at room temp for 2 hrs. The reaction mixture was filtered through a CELITE.(R). pad and the filtrate evaporated under reduced pressure. The residue was taken up in Et2O (about 200 mL), washed with brine then dried over MgSO4. Evaporation of the solvent afforded 2.66 g (42percent) of 2a as a dark liquid.step 2 2-BROMO-6-METHYLANILINE (2a) -A mixture of tellurium (21.6 g, 169.4 mmol) and NaBH4 (15.0 g, 396 mmol) in 575 mL of absolute ETOH was heated at reflux under an atmosphere of N2 for 1 hr, then allowed to cool to rt. A solution of 3-bromo-2- nitrotoluene (LC ; 7.32g, 33.8 mmol) in 25 mL ETOH was added all at once and the mixture allowed to stir at room temperature for 2 hrs. The reaction mixture was filtered through a CELITE (D pad and the filtrate evaporated under reduced pressure. The residue was taken up in ET20 (about 200 mL), washed with brine then dried over MGS04. Evaporation of the solvent afforded 2.66g (42percent) of 2a as a dark liquid.Add 0.5mmol o-toluidine (1c) to 4mL of water, Add 0.125 mmol copper acetate to it, 1.0mmol potassium bromide, 1.0mmol hydrogen peroxide, Reaction at room temperature for 2 hours, After the reaction is over, Saturated aqueous NaCl solution was added to the reaction solution.Extract with ethyl acetate, The organic layer was dried over anhydrous magnesium sulfate.filter, 60 °C evaporated to dryness, That is, a crude product of the compound represented by the formula (2c) is obtained.The crude product of the compound represented by the formula (2c) is subjected to silica gel column chromatography.With a volume ratio of ethyl acetate and petroleum ether1:4 solution is mobile phase, The TLC tracked the elution with an Rf of 0.3-0.5.The collected eluate was removed under reduced pressureSolvents, dry, A pure product of the formula 36 (2c) was obtained.Yield 39percent.1) 12mL concentrated sulfuric acid was added to 20mL aqueous solution, heated to 85 , 26g of 2-methylaniline (1) was slowly added and the mixture was heated and stirred for 15 minutes.Swirl to the water. Argon atmosphere, heated to 250 ° C, continued reaction 13h.After the temperature was lowered to room temperature, 200 mL of 10percent aqueous sodium hydroxide solution was added, Heated to 90 , 30 minutes after the reaction was cooled and filtered.The filtrate was adjusted to pH = 1 with concentrated sulfuric acid to precipitate a large amount of solid, filtered, 45 g of sulfonic acid methylaniline (2) were obtained;The resulting 45 g of product (2) was then treated with 500 mL of N, N-dimethylformamide solution, And 9.0 mL of liquid bromine (dissolved in 50 mL of N, N-dimethylformamide)The reaction was continued for 4 hours at room temperature to give 40 gBrilliant red solid bromosulfonylmethylaniline (3);Then 40 g of product (3) and 350 mL of 11percent hydrochloric acid were added to a 500 mL single neck flask, Heated to reflux for 11 hours, cooled to room temperature, Neutralized to pH = 8 with saturated sodium carbonate, extracted with ethyl acetate, Dried over anhydrous sodium sulfate and filtered to give 13.8 gBromo-2-methylaniline (4) as a yellow solid

Molecular Weight:186.05
XLogP3:2.3
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Exact Mass:184.98401
Monoisotopic Mass:184.98401
Topological Polar Surface Area:26
Heavy Atom Count:9
Complexity:94.9
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes