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ChemicalBook CAS DataBase List 2-AMINO-5-METHYLPHENYBORONIC ACID, PINACOL ESTER
948592-80-1

2-AMINO-5-METHYLPHENYBORONIC ACID, PINACOL ESTER synthesis

3synthesis methods
-

Yield:948592-80-1 94%

Reaction Conditions:

with dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2;potassium acetate in dimethyl sulfoxide at 80;Inert atmosphere;

Steps:

119A 11 9A. Preparation of 4-methyl-2-(4,4,5 ,5 -tetramethyl- 1,3 ,2-dioxaborolan-2-yl)aniline

2-Bromo-4-methylaniline (3 g, 16.12 mmol), bis(pinacolato)diboron (6.14 g,24.19 mmol), KOAc (4.07 g, 41.4 mmol) were added to DMSO (9 mL) under N2 atm and then degassed for 10 mm. Pd(dppf)C12.CH2Cl2Adduct (0.395 g, 0.484 mmol) was added and the resulting suspension was stirred overnight at 80 °C. The reaction mixture was partitioned between DCM and water. The organic layer was washed with brine, dried over Na2SO4, filtered, and concentrated then purified normal phase chromatography usinghexane and EtOAc as eluents to give 4-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (3.52 g, 94% yield) as a clear oil which solidified into a white solid upon standing. MS(ESI) m/z: 152.3 (M-C6H,o+H). ‘H NMR (400MHz, CDC13-d) ? 7.43 (d, J=1.8 Hz, 1H), 7.04 (dd, J=8.3, 2.3 Hz, 1H), 6.55 (d, J=8.1 Hz, 1H), 4.60 (br. s., 2H), 2.23- 2.20 (m, 3H), 1.38 - 1.32 (m, 12H).

References:

WO2015/116886,2015,A1 Location in patent:Page/Page column 351

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