Hydrochloric Acid → Benzyl N-(2-aminoethyl)carbamate hydrochloride

Under an atmosphere of dry argon, 24.3 g (0.128 mol) of N-CBZ-aminoacetonitrile (1e) was dissolved in anhydrous tetrahydrofuran (32 ml). The solution was stirred and 64 ml of borane-methylsulfide complex (2M in tetrahydrofuran) was added via syringe. The mixture was heated to reflux and stirred overnight. The mixture was cooled with an ice bath as 5 ml of water was added slowly, with vigorous stirring. The stirring was continued for ca. 5 minutes, then 75 ml of 6M HCl was slowly added. The mixture was stirred for 1 hour, then the excess tetrahydrofuran and dimethyl sulfide was removed in vacuo . The aqueous residue was extracted with ether (2×50 ml). The ether extracts were then discarded. The pH of the aqueous residue was raised to 11 by adding concentrated NH4OH. The resulting aqueous solution was extracted with ethyl acetate (3×100 ml) and the ethyl acetate extracts were combined and washed with brine (50 ml). After drying over anhydrous magnesium sulfate, the solution was filtered and concentrated in vacuo. The resulting oil was dissolved in 30 ml of anhydrous methanol, treated with cold methanolic HCl and concentrated in vacuo to produce a solid. The solid was triturated with ether and collected by filtration to give 15.1 g (51% yield) of N-CBZ-ethylenediamine hydrochloride (1f) as a white powder. 1H NMR(D2O) δ 3.15(m, 2H), 3.46(m, 2H), 5.14(s, 2H), 7.46(bs, 5H); 13C NMR (D2O) δ 41.1, 42.6, 70.4, 131.0, 131.3, 131.7, 132.0, 139.4, 161.7.

1. temperatureThe mixture was heated
2. temperatureto reflux
3. stirringstirred overnight
4. additionwas added slowly, with vigorous stirring
5. stirringThe mixture was stirred for 1 hour
6. customthe excess tetrahydrofuran and dimethyl sulfide was removed in vacuo
7. extractionThe aqueous residue was extracted with ether (2×50 ml)
8. temperatureThe pH of the aqueous residue was raised to 11
9. additionby adding concentrated NH4OH
10. extractionThe resulting aqueous solution was extracted with ethyl acetate (3×100 ml)
11. washwashed with brine (50 ml)
12. dry with materialAfter drying over anhydrous magnesium sulfate
13. filtrationthe solution was filtered
14. concentrationconcentrated in vacuo
15. dissolutionThe resulting oil was dissolved in 30 ml of anhydrous methanol
16. additiontreated with cold methanolic HCl
17. concentrationconcentrated in vacuo
18. customto produce a solid
19. customThe solid was triturated with ether
20. filtrationcollected by filtration

ORDレコード

ord-c017b4f5bea34aa8b28b509ea2e77867

出典データセット

uspto-grants-1997_01

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US05594106