(E)-but-2-en-1-amine;hydrochloride

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of (E)-2-buten-1-amine HCl (5.37 g, 49.9 mmol) (Chem. Ber. 117, 1250(1984) in acetonitrile (100 mL) was treated with methyl bromoacetate (4.72 mL, 49.9 mmol) and Et3N (14.0 mL, 99.8 mmol) and stirred at room temperature for I hour. The suspension was then heated at reflux overnight. Solution occurred at reflux temperature. After cooling, the precipitated Et3N.HCl was filtered off and the solvent removed under reduced pressure leaving 5.0 g of the crude product. Chromatography on silica gel, eluting with CHCl3/MeOH (98/2) gave 1.41 g (19.8% yield) of the pure product as an oil. The suspension was then heated at reflux overnight at reflux temperature After cooling the precipitated Et3N.HCl was filtered off the solvent removed under reduced pressure leaving 5.0 g of the crude product Chromatography on silica gel, eluting with CHCl3/MeOH (98/2)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of (E)-2-buten-1-amine HCl (5.37 g, 49.9 mmol) (Chem. Ber. 117, 1250(1984) in acetonitrile (100 mL) was treated with methyl bromoacetate (4.72 mL, 49.9 mmol) and Et3N (14.0 mL, 99.8 mmol) and stirred at room temperature for I hour. The suspension was then heated at reflux overnight. Solution occurred at reflux temperature. After cooling, the precipitated Et3N.HCl was filtered off and the solvent removed under reduced pressure leaving 5.0 g of the crude product. Chromatography on silica gel, eluting with CHCl3/MeOH (98/2) gave 1.41 g (19.8% yield) of the pure product as an oil. The suspension was then heated at reflux overnight at reflux temperature After cooling the precipitated Et3N.HCl was filtered off the solvent removed under reduced pressure leaving 5.0 g of the crude product Chromatography on silica gel, eluting with CHCl3/MeOH (98/2)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Benzyl carbonochloridate (22.8 mL, 167 mmol) was added to a solution of (2E)-but-2-en-1-amine hydrochloride (12.0 g, 112 mmol) and Hunig's base (43.2 g, 330 mmol) in acetonitrile (120 mL) under a nitrogen atmosphere at 0° C. The reaction mixture was stirred under nitrogen at 0° C. for 1 hour and then allowed to warm to ambient temperature. After 3 hours, the reaction mixture was diluted with brine (50 mL) and was extracted with ethyl acetate (3×50 mL). The organic layers were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to afford the crude product residue. The crude product residue was purified by silica gel chromatography (ethyl acetate/petroleum ether) to give benzyl (2E)-but-2-en-1-ylcarbamate. MS ESI calc'd. for C12H16NO2 [M+H]+ 206. found 206. to warm to ambient temperature After 3 hours was extracted with ethyl acetate (3×50 mL) dried over sodium sulfate filtered concentrated under reduced pressure to afford the crude product residue The crude product residue was purified by silica gel chromatography (ethyl acetate/petroleum ether)

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 150 mg (0.57 mmol) of 4-allylamino-2-chloro-6-nitroquinazoline was dissolved in 2 ml of acetonitrile, and 305 mg (2.83 mmol) of trans-2-butenylamine hydrochloride and 0.39 ml (2.83 mmol) of triethylamine were added thereto, followed by stirring at 50° C. for 6 hours. To the reaction solution was water added, followed by extraction with ethyl acetate, washing with brine and drying over anhydrous sodium sulfate. After the solvent was distilled off, the residue was purified by a silica gel column to give 138 mg (yield: 80.9%) of the title compound. added followed by extraction with ethyl acetate washing with brine drying over anhydrous sodium sulfate After the solvent was distilled off the residue was purified by a silica gel column

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of (E)-2-buten-1-amine HCl (5.37 g, 49.9 mmol) (Chem. Ber. 117, 1250(1984) in acetonitrile (100 mL) was treated with methyl bromoacetate (4.72 mL, 49.9 mmol) and Et3N (14.0 mL, 99.8 mmol) and stirred at room temperature for I hour. The suspension was then heated at reflux overnight. Solution occurred at reflux temperature. After cooling, the precipitated Et3N.HCl was filtered off and the solvent removed under reduced pressure leaving 5.0 g of the crude product. Chromatography on silica gel, eluting with CHCl3/MeOH (98/2) gave 1.41 g (19.8% yield) of the pure product as an oil. The suspension was then heated at reflux overnight at reflux temperature After cooling the precipitated Et3N.HCl was filtered off the solvent removed under reduced pressure leaving 5.0 g of the crude product Chromatography on silica gel, eluting with CHCl3/MeOH (98/2)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Benzyl carbonochloridate (22.8 mL, 167 mmol) was added to a solution of (2E)-but-2-en-1-amine hydrochloride (12.0 g, 112 mmol) and Hunig's base (43.2 g, 330 mmol) in acetonitrile (120 mL) under a nitrogen atmosphere at 0° C. The reaction mixture was stirred under nitrogen at 0° C. for 1 hour and then allowed to warm to ambient temperature. After 3 hours, the reaction mixture was diluted with brine (50 mL) and was extracted with ethyl acetate (3×50 mL). The organic layers were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure to afford the crude product residue. The crude product residue was purified by silica gel chromatography (ethyl acetate/petroleum ether) to give benzyl (2E)-but-2-en-1-ylcarbamate. MS ESI calc'd. for C12H16NO2 [M+H]+ 206. found 206. to warm to ambient temperature After 3 hours was extracted with ethyl acetate (3×50 mL) dried over sodium sulfate filtered concentrated under reduced pressure to afford the crude product residue The crude product residue was purified by silica gel chromatography (ethyl acetate/petroleum ether)