تفاعل #2145489

معادلة التفاعل

benzyl chloroformate

Sodium hydroxide

ethylenediamine

Bromophenol Blue

hydrochloric acid

→

benzyl N-(2-aminoethyl)carbamate

المردود 54.0%

المذيبات

ether

methanol

water

ظروف التفاعل

المعالجة

1. 1
   workup.ADDITION(addition time 1.75 hours)
2. 2
   درجة الحرارةto maintain the solution at pH 3.0-4.5
3. 3
   أخرىThe methanol was removed at reduced pressure
4. 4
   ترشيحthe reaction mixture was filtered
5. 5
   استخلاصThe aqueous filtrate was extracted once with benzene
6. 6
   استخلاصthe benzene extract
7. 7
   درجة الحرارةThe aqueous solution was cooled in a salt-ice bath
8. 8
   workup.ADDITIONtreated with sodium hydroxide (130 ml, 10 N) to pH 11-13
9. 9
   أخرىThree layers formed
10. 10
    أخرىThe aqueous layer was separated
11. 11
    استخلاصextracted four times with portions of ether
12. 12
    أخرىthe ether removed
13. 13
    أخرىwas then used at 25° C. until the pressure
14. 14
    workup.ADDITIONdropped to 0.6 ppm
15. 15
    أخرىDuring this time, water and ethylenediamine were removed by distillation
16. 16
    workup.WAITThe residue left in the flask
17. 17
    ترشيحAfter the mixture was filtered

الإجراء التجريبي

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.

المصدر