Borane → 2-(Aminomethyl)-5-bromoaniline

Temperature

0 °C

To a solution of compound (11) (2 g, 10.0 mmol) in dry THF at 0° C. under an argon atmosphere was slowly added borane (15 mL, 1.0 M in THF). The reaction mixture was stirred for 10 min at 0° C. and further 72 h at room temperature. The reaction mixture was cooled to 0° C. and quenched by addition of ethanol (96%). The resulting suspension was extracted with ethyl acetate (3×20 mL). The combined organic layers were dried over sodium sulfate. Ethyl acetate was completely removed under reduced pressure and the residues were chromatographed over silica column, eluting with ethyl acetate:hexanes (1:1) and changing to (100%) afforded 1.73 g (85%) of compound (12) as a dark brown thick gum. IR (KBr) νmax. cm−1: 3438, 3318 (NH2), 3052 (Ar—H), 2911 (Alph-H), 1604, 1512, 1416 (C═C). 1H NMR (500 MHz, CDCl3) δ=4.19 (s, 2H, NH2); 4.42 (s, 2H, CH2); 6.52 (d, 1H, J=8.2 Hz, H-3); 7.16 (dd, 1H, J=2.2, 8.2 Hz, H-4); 7.18 (d, 1H, J=2.2 Hz, H-6); 13C NMR (125.7 MHz, CDCl3) δ=63.78 (CH2), 109.56 (C-2), 117.51 (C-6), 126.57 (C-5), 131.58 (C-3/C-4), 131.86 (C-3/C-4), 145.06 (C-1). Calculated (%) for C7H9BrN2 (199.99); C: 41.82, H: 4.51, N: 13.93. found (%); C: 41.74, H: 4.58, N: 13.84.

1. customat 0° C.
2. temperatureThe reaction mixture was cooled to 0° C.
3. customquenched by addition of ethanol (96%)
4. extractionThe resulting suspension was extracted with ethyl acetate (3×20 mL)
5. dry with materialThe combined organic layers were dried over sodium sulfate
6. customEthyl acetate was completely removed under reduced pressure
7. customthe residues were chromatographed over silica column
8. washeluting with ethyl acetate:hexanes (1:1)

ORD record

ord-76e2e5c22cdc4dc7bad578b9eb9d2f52

Source dataset

uspto-grants-2015_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09073900B2