4-chlorobut-2-yn-1-amine;hydrochloride

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Amino-4-chloro-2-butyne hydrochloride (59.75 g) was dissolved in 10% aqueous sodium acetate-solution (335 ml). Ethyl acetate (500 ml) was added, and acetic anhydride (70 ml) was added dropwise at room temperature. A 25% aqueous sodium acetate solution was added to pH 5 and the solution was stirred for 30 min at room temperature. The ethyl acetate layer was separated, and the aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with water, brine and dried over sodium sulphate, filtered and evaporated in vacuo yielding 1-acetylamino4-chloro-2-butyne as a yellow syrup (58.8 g). The ethyl acetate layer was separated the aqueous layer was extracted twice with ethyl acetate The combined organic layers were washed with water, brine dried over sodium sulphate filtered evaporated in vacuo

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Ex-8c) 14.1 g of 1-Amino-4-chloro-2-butyne hydrochloride was taken up in 70 mL of dioxane and :35 mL water. 4 g NaOH was added and the reaction mixture was stirred for 30 minutes followed by the addition of 21.8 g di-t-butylcarbonate at 20° C. The reaction mixture was stirred at 20° C. to 25° C. for 8 h and then the lower organic layer was separated. The upper aqueous layer was extracted with 100 mL of dichloromethane. Organic layers were combined and washed with 50% aqueous NaHCO3, dried over anhydrous MgSO4, treated with Darco, filtered over celite and concentrated to give a brown oil. This oil was chromatographed to give 9 g of 1-t-Butyloxycarbonylamino-4-chloro-2-butyne as a white solid. The reaction mixture was stirred at 20° C. to 25° C. for 8 h the lower organic layer was separated The upper aqueous layer was extracted with 100 mL of dichloromethane washed with 50% aqueous NaHCO3 dried over anhydrous MgSO4 treated with Darco filtered over celite and concentrated to give a brown oil This oil was chromatographed