Research on new synthetic routes about 3-Bromo-5-methylaniline

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 3-Bromo-5-methylaniline, and friends who are interested can also refer to it.

Application of 74586-53-1, As we all know, there are many different methods for the synthesis of a compound, and people can choose the synthesis method that suits their own laboratory according to the actual situation. 74586-53-1 name is 3-Bromo-5-methylaniline, This compound is widely used in many fields, so it is necessary to find a new synthetic route. The downstream synthesis method of this compound is introduced below.

Dioxane (720 mL) in a 1 L three-necked round bottom flask was degassed for 30 minutes. 3-Bromo-5-methylaniline (60 g, 193 mmol), (bispinacolato)diboron (96 g, 377 mmol), potassium acetate (42.7 g, 435 mmol), X-Phos (8.3 g, 17.41 mmol) and tris(dibenzylideneacetone)dipalladium(0) (3.99 g, 4.35 mmol) were added to the degassed solvent. After stirring for 10 minutes at room temperature, the reaction was heated to an internal temperature of 80 C. After 4 hours, the heating mantle was removed and replaced with an ice water bath. The reaction mixture was cooled to 30 C, and was then filtered through a pad of CELITE (washing with 500 mL of methyl tert-butyl ether). This was transferred to a 4 L seperatory funnel containing 500 mL pH 8 phosphate buffer, 500 mL brine, and an additional 500 mL of methyl tert-butyl ether. The layers were cut and the organic washed with 1 L of a 1 : 1 mixture of brine and water. The aqueous layers combined and were sequentially back extracted with a second 500 mL portion of methyl tert-butyl ether. The combined organics were treated with 100 g of magnesium sulfate and the resulting mixture stirred for 20 minutes. This was then filtered and concentrated under reduced pressure. The resultant residue was purified by flash chromatography (0-25% ethyl acetate in hexanes) to yield 3-methyl-5-(4,4,5,5-tetramethyl-l,3,2- dioxaborolan-2-yl)aniline as a light orange solid. MS ESI calc’d. for C 3H21B O2 [M + H]+ 234, found 234.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 3-Bromo-5-methylaniline, and friends who are interested can also refer to it.

Reference:
Patent; MERCK SHARP & DOHME CORP.; MERCK CANADA INC.; ANTHONY, Neville, J.; ANDRESEN, Brian, M.; NORTHRUP, Alan, B.; CHILDERS, Kaleen, K.; DONOFRIO, Anthony; MILLER, Thomas, A.; LIU, Yuan; MACHACEK, Michelle, R.; WOO, Hyun Chong; SPENCER, Kerrie, B.; ELLIS, John Michael; ALTMAN, Michael, D.; ROMEO, Eric, T.; GUAY, Daniel; GRIMM, Jonathan; LEBRUN, Marie-Eve; ROBICHAUD, Joel, S.; WANG, Liping; DUBOIS, Byron; DENG, Qiaolin; WO2014/176210; (2014); A1;,
Bromide – Wikipedia,
bromide – Wiktionary