Allyl chloroformate → HCID 18329264, compound

Temperature

0 °C

Mono-t-butyloxycarbonyl (BOC) 1,5-pentanediamine was synthesized by using 1,5-diaminopentane (12.5 g, 122 mmol) in place of 1,3-diaminopropane in the synthesis of mono-allyloxycarbonyl-1,3-diaminopropane described in Example 1 above, yielding 10 g (49 mmol) of mono-tert-butyloxycarbonyl-1,5-diaminopentane (1). The mono-tert-butyloxycarbonyl-1,5-diaminopentane (1) (5.8 g, 28.7 mmol) was dissolved in 75 mL of dichloromethane with 7.5 mL of diisopropylethylamine and cooled to 0° C. A solution of allyl chloroformate (3.3 mL) in dichloromethane (25 mL) was added over five minutes. The reaction was allowed to warm to room temperature for one hour and then solvent was removed by rotary evaporation. The residue was dissolved in 100 mL of ethyl acetate and washed with three 100 mL portions of 10% citric acid, once with 100 mL saturated aqueous sodium bicarbonate and once with 100 mL of saturated aqueous sodium chloride. The organic phase was dried over magnesium sulfate and solvent was removed by rotary evaporation. The resulting oil (2) was treated with 25 mL of trifluoroacetic acid for 30 minutes. The trifluoroacetic acid was removed by rotary evaporation and the resulting reside was twice dissolved in dichloromethane and then evaporated to remove residual solvent. The residue was dissolved in 50 mL of 3N hydrochloric acid and washed with two 50 mL portions of dichloromethane. The aqueous phase was cooled in an ice bath and the pH was adjusted to approximately 13 with 50% aqueous sodium hydroxide. The basic aqueous phase was extracted with three 100 mL portions of dichloromethane, the combined organics were washed with 100 mL of saturated aqueous sodium chloride and then dried over potassium carbonate. The mixture was filtered, the solvent removed first by rotary evaporation and then by high vacuum to yield 3.95 g of mono-allyloxycarbonyl-1,5-diaminopentane (3) as a colorless oil.

1. temperatureto warm to room temperature for one hour
2. customsolvent was removed by rotary evaporation
3. dissolutionThe residue was dissolved in 100 mL of ethyl acetate
4. washwashed with three 100 mL portions of 10% citric acid, once with 100 mL saturated aqueous sodium bicarbonate and once with 100 mL of saturated aqueous sodium chloride
5. dry with materialThe organic phase was dried over magnesium sulfate and solvent
6. customwas removed by rotary evaporation
7. additionThe resulting oil (2) was treated with 25 mL of trifluoroacetic acid for 30 minutes
8. customThe trifluoroacetic acid was removed by rotary evaporation
9. dissolutionthe resulting reside was twice dissolved in dichloromethane
10. customevaporated
11. customto remove residual solvent
12. dissolutionThe residue was dissolved in 50 mL of 3N hydrochloric acid
13. washwashed with two 50 mL portions of dichloromethane
14. temperatureThe aqueous phase was cooled in an ice bath
15. extractionThe basic aqueous phase was extracted with three 100 mL portions of dichloromethane
16. washthe combined organics were washed with 100 mL of saturated aqueous sodium chloride
17. dry with materialdried over potassium carbonate
18. filtrationThe mixture was filtered
19. customthe solvent removed first by rotary evaporation

ORD record

ord-34bc4761a7cd465caa54182ca658041d

Source dataset

uspto-grants-2001_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06271198B1