Diisopropylamine → Thieno[3,2-C]pyridine-2-carbaldehyde

Beteiligte Stoffe

Reaktionsbedingungen

Reaktionsschritte

A solution of 1.6 g (15.8 mMoles) of diisopropylamine in 50 ml of dry THF was stirred under a nitrogen blanket and cooled to -25° C. The reaction solution was then diluted by the addition of 9.6 ml of a 1.6 Molar hexane solution of n-butyl lithium. The reaction mixture was stirred for twenty minutes at -25° C., and then was cooled to -70° C. and diluted by the dropwise addition of a solution of 1.7 g (13 mMoles) of thieno[3,2-c]pyridine in 50 ml of THF (temperature was maintained at -70° to -65° C. throughout the addition). Following complete addition of the thienopyridine, the reaction mixture was stirred at -70° C. for twenty minutes. A solution of 2.0 ml of N,N-dimethylformamide in 25 ml of THF was next added to the reaction mixture, and stirring was then continued at -70° C. for twenty minutes, and for an additional thirty minutes at -40° C. The reaction was quenched by the addition of 3 ml of glacial acetic acid, and then the mixture was warmed to 0° C. The reaction solvent was removed by evaporation under reduced pressure to provide the product as a crude oil. The oil was dissolved in water containing 1N hydrochloric acid to pH 1.0. The aqueous acid solution was extracted with dichloromethane, and then made alkaline to pH 11.5 with 1N sodium hydroxide. The alkaline solution was extracted several times with fresh dichloromethane, and the extracts were combined, dried, and the solvent was removed by evaporation under reduced pressure. Crystallization of the product thus formed from 500 ml of hot hexane afforded 800 mg of 2-formylthieno[3,2-c]pyridine.

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