反应详情

A stirred solution of 4-(4-chlorophenylthio)-3,5-dichlorobenzylamine (3.59 g, 11.3 mmol) in absolute ethanol (30 ml) at ambient temperature was treated in one portion with 2,4,6-triphenylpyrylium tetrafluoroborate (3.58 g, 9.06 mmol). The mixture was stirred 30 minutes, diluted with dimethylformamide (30 ml), and stirred 16 hours. The solvent was evaporated under vacuum at 60° C. and the residue was triturated with diethyl ether (2×25 ml). The residual solid was dissolved in dry dimethylformamide (23 ml), dry sodium azide (2.27 g, 34.9 mmol) was added, and the mixture was stirred at 130° C. for 6 hours and ambient temperature for 4 days. The mixture was diluted with water (250 ml) and extracted twice with diethyl ether. The combined extracts were washed with water (2X) and brine, dried over anhydrous magnesium sulfate, and evaporated under vacuum. The residue was disolved in dichloromethane, silica gel (60 g) was added, and the mixture was dried under vacuum, placed on a column of silica gel (600 ml), and eluted in 50 ml fractions with 1:2 (v/v) dichloromethane-hexane. After a forerun, fractions 8-14 were combined and evaporated under vacuum to provide 320 mg oily 4-(4-chlorophenylthio)-3,5-dichlorobenzyl azide. Fractions 15-22 were combined, evaporated under vacuum, and the residue was chromatographed on one 20 cm×20 cm 1500μ silica gel preparative thick layer chromatography plate developed with 1:2 (v/v) dichloromethanehexane. Product was eluted with dichloromethane and solvent was evaporated under vacuum to provide an additional 62 mg of oily azide (total yield: 382 mg [10%]).

1. stirringstirred 16 hours
2. customThe solvent was evaporated under vacuum at 60° C.
3. customthe residue was triturated with diethyl ether (2×25 ml)
4. dissolutionThe residual solid was dissolved in dry dimethylformamide (23 ml)
5. stirringthe mixture was stirred at 130° C. for 6 hours and ambient temperature for 4 days
6. extractionextracted twice with diethyl ether
7. washThe combined extracts were washed with water (2X) and brine
8. dry with materialdried over anhydrous magnesium sulfate
9. customevaporated under vacuum
10. additionsilica gel (60 g) was added
11. customthe mixture was dried under vacuum
12. washeluted in 50 ml fractions with 1:2 (v/v) dichloromethane-hexane
13. customevaporated under vacuum