5-Bromo-2-isopropoxyaniline synthesis

Yield:1019442-22-8 64%

Reaction Conditions:

with hydrogenchloride;tin(ll) chloride in tetrahydrofuran;water at 50; for 24 h;

Steps:

Bromo-isopropoxy amine (general procedure 3)

General procedure: To a solution of 4-bromo-1 -isopropoxy-2-nitrobenzene (prepared using general procedure 1 , 84%, 17.54 g, 67.4 mmol) in THF (270 mL), HCI (1 M aq, 270 mL, 270 mmol, 4.0 eq) and stannous chloride (38 g, 282 mmol, 3.0 eq) were added and heated to 50°C for 24 hours. Upon completion, the mixture was quenched with saturated aqueous sodium bicarbonate, filtered over celite, and the crude product was extracted twice with ethyl acetate. The combined organic layers were dried (Na₂S0₄), concentrated, and purified by combiflash 0 to 30% EtOAc to yield bromo-isopropoxy amine (9.93 g, 64% yield) ¹ H NMR (400 MHz, CDCI3): δ 6.82 p.p.m. (d, J=2.4 Hz, 1 H), 6.77 (dd, J1=8.5 Hz, J2=2.4 Hz, 1 H), 6.63 (d, J=8.6 Hz, 1 H), 4.46 (hept, J=1 .5 Hz, 1 H), 1 .33 (d, J=6.0, 6H), ¹³C NMR (125 MHz): δ 1 14.4, 138.9, 120.6, 1 17.6, 1 14.8, 1 13.2, 71 .0 HRMS (m/z): [M+] calculated for C9H13NOBr 230.1 , found 229.01

References:

WO2014/11973,2014,A2 Location in patent:Paragraph 0157; 0162