反应详情

Raney Nickel (1 g) and hydrazine hydrate (3 ml) was added to ethyl 5-nitrobenzo[b]thiophene-2-carboxylate (25 g) (obtained as described in Syn. Comm., (1991), 21, 959-964) in ethanol (500 ml) at 60° C. A vigorous reaction ensued and the mixture refluxed. Further portions of Raney Nickel (1 g) and hydrazine hydrate (3 ml) were added at 10 minute intervals until a total of 15 ml had been added and the mixture was then refluxed for 90 minutes. The hot mixture was filtered and the filtrate evaporated. The residue was dissolved in hot ethanol (300 ml) and activated charcoal was added. The mixture was filtered and the filtrate evaporated to dryness to give ethyl 5-aminobenzo[b]thiophene-2-carboxylate (18 g) as a pale yellow solid. The solid was added to a stirred mixture of concentrated hydrochloric acid (50 ml) and water (130 ml) at -0C. A solution of sodium nitrite (5.6 g) in water (20 ml) was added slowly and then the mixture was allowed to stir at 0° C. for a further 30 minutes. A solution of potassium iodide (130 g) in water (200 ml) was then added. The mixture was allowed to warm to ambient temperature and then heated at 50° C. for 30 minutes. The mixture was allowed to cool, extracted with chloroform (150 ml) and the organic layer washed with sodium metabisulphite solution. The organic phase was dried (MgSO4) and evaporated to give a brown oil. The oil was purified by chromatography on silica using a gradient of hexane increasing to 10% ethyl acetate/hexane. The appropriate fractions were combined and evaporated to give ethyl 5-iodobenzo[b]thiophene-2-carboxylate (14 g) as an oil; NMR (d6 -DMSO): 1.35 (t, 3H), 4.4 (q, 2H), 7.8 (dd, 1H), 7.9 (d, 1H), 8.15 (s, 1H), 8.45 (d, 1H).

1. temperatureA vigorous reaction ensued and the mixture refluxed
2. additionhad been added
3. temperaturethe mixture was then refluxed for 90 minutes
4. filtrationThe hot mixture was filtered
5. customthe filtrate evaporated
6. dissolutionThe residue was dissolved in hot ethanol (300 ml)
7. additionactivated charcoal was added
8. filtrationThe mixture was filtered
9. customthe filtrate evaporated to dryness