1-Bromo-4-nitrobenzene → HCID 19925614, compound

Participants

Reaction Steps

A 500 mL round bottomed flask equipped with a magnetic stirbar was charged with sodium hydride (3.78 g of a 60% oil dispersion, 95 mmol), and freshly dried THF (200 mL) under a stream of nitrogen. To the stirred suspension was added t-butanol (8 mL). When hydrogen gas evolution ceased, m-bromobenzenethiol (12.0 g, 63 mmol) was via syringe over 5 rain and the resulting solution was stirred for 10 min. To this solution was added in a single portion p-nitrobromobenzene (10.7 g, 52.9 mmol). The solution was stirred at room temperature for 45 min and sodium hydride (0.5 g of a 60% oil dispersion, 12.5 mmol) was added. After 30 min m-bromobenzenethiol (1.0 mL, 9.7 mmol) was added and the reaction was judged to be complete 30 min later by tlc. The reaction mixture was partitioned between saturated aqueous ammonium chloride and ethyl acetate. The layers were separated and the aqueous layer was extracted with ethyl acetate (3 x, 100 mL). The combined organic extracts were washed (1x, 15% aqueous sodium hydroxide; 2x, brine), dried (Na2SO4), filtered and concentrated in vacuo to to ~400 mL. Decolorizing carbon was added to the organic extracts and the solution was filtered through a celite pad as and concentrated in vacuo to give the unpurified product as an orange solid (19.4 g). The solid was taken up in ether and treated with decolorizing carbon, filtered through celitc, and the volatiles removed in vacuo. Two recrystallizations from ether/hexanes provided pure 3-(p-nitrobenzenethioxy)bromobenzene.

Provenance & Evidence