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

温度

25 °C

A mixture of ethylenediamine (60 g, 1 mole), water (250 ml), methanol (500 ml) and Bromophenol Blue solution was acidified to pH 3 (yellow color) with hydrochloric acid (165 ml, 12 N). While the resulting solution was vigorously stirred at 25° C., benzyl chloroformate (100.6 g, 0.59 mole) was added dropwise (addition time 1.75 hours). Sodium hydroxide (210 ml, 5 N) was added as required to maintain the solution at pH 3.0-4.5. The methanol was removed at reduced pressure and the reaction mixture was filtered. The aqueous filtrate was extracted once with benzene, and the benzene extract was discarded. The aqueous solution was cooled in a salt-ice bath, layered with ether and treated with sodium hydroxide (130 ml, 10 N) to pH 11-13. Three layers formed: an ether layer, an aqueous layer, and an oily blue layer. The aqueous layer was separated and extracted four times with portions of ether. The ether layer and ether extracts were combined with the oily blue layer and the ether removed using water pump vacuum. An oil pump was then used at 25° C. until the pressure dropped to 0.6 ppm. During this time, water and ethylenediamine were removed by distillation. The residue left in the flask consisted of an oil and a small amount of solid. After the mixture was filtered, 60 g (54% yield) of benzyl N-(2-aminoethyl)carbamate were obtained. This crude oil worked satisfactorily in the next step without further purification. See C. M. Hoffmann and S. R. Sapir, Journal of Organic Chemistry, 27, 3565 (1962) for further discussion of this preparatory method.

1. addition(addition time 1.75 hours)
2. temperatureto maintain the solution at pH 3.0-4.5
3. customThe methanol was removed at reduced pressure
4. filtrationthe reaction mixture was filtered
5. extractionThe aqueous filtrate was extracted once with benzene
6. extractionthe benzene extract
7. temperatureThe aqueous solution was cooled in a salt-ice bath
8. additiontreated with sodium hydroxide (130 ml, 10 N) to pH 11-13
9. customThree layers formed
10. customThe aqueous layer was separated
11. extractionextracted four times with portions of ether
12. customthe ether removed
13. customwas then used at 25° C. until the pressure
14. additiondropped to 0.6 ppm
15. customDuring this time, water and ethylenediamine were removed by distillation
16. waitThe residue left in the flask
17. filtrationAfter the mixture was filtered

ORDレコード

ord-2883450f8a384b4594c5885611466923

出典データセット

uspto-grants-1982_08

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US04346231