Reaction #362828

Reaction equation

water

allylbromide

triethylamine

diethyl 4-aminobenzylacetamidomalonate

DMF

allyl bromide

triethylamine

→

diethyl 4-diallylaminobenzylacetamidomalonate

diethyl 4-allylaminobenzylacetamidomalonate

Conditions

Workup

1. 1
   Otherare placed in a three-necked flask
2. 2
   Otherwhich is surmounted with a dropping funnel
3. 3
   Temperaturemaintained under a nitrogen atmosphere
4. 4
   workup.STIRRINGAfter stirring for 19 h
5. 5
   workup.STIRRINGthe mixture is stirred for 26 h
6. 6
   Extractionthis mixture is extracted with 1 l of ethyl acetate
7. 7
   OtherThe aqueous phase is separated off after settling
8. 8
   Washwashed with 2 times 500 ml of ethyl acetate
9. 9
   Washwashed with 500 ml of distilled water
10. 10
    Otherseparated off
11. 11
    Dryingdried over magnesium sulphate
12. 12
    Filtrationfiltered
13. 13
    Concentrationconcentrated to dryness in order
14. 14
    Otherto yield a chestnut oil
15. 15
    Otherthis oil is purified by flash chromatography (eluant, CH2Cl290/AcOEt 10) in order

Procedure

10 g of diethyl 4-aminobenzylacetamidomalonate dissolved in 150 ml of DMF are placed in a three-necked flask which is surmounted with a dropping funnel and maintained under a nitrogen atmosphere. 6.57 ml of allyl bromide, and then 10.76 ml of triethylamine, are added slowly, at room temperature and while stirring. After stirring for 19 h, a further 1.31 ml of allylbromide and 2.15 ml of triethylamine are then added and the mixture is stirred for 26 h. The reaction medium is poured onto 1.5 l of distilled water and this mixture is extracted with 1 l of ethyl acetate. The aqueous phase is separated off after settling and washed with 2 times 500 ml of ethyl acetate. The organic phases are combined, washed with 500 ml of distilled water and then with 500 ml of water which is saturated with sodium chloride, separated off, dried over magnesium sulphate, filtered and then concentrated to dryness in order to yield a chestnut oil; this oil is purified by flash chromatography (eluant, CH2Cl290/AcOEt 10) in order to yield 6.66 g of diethyl 4-diallylaminobenzylacetamidomalonate in the form of a beige solid which melts at 94-96° C. (Rf=0.6, AcOEt 50/cyclohexane 50) and 3.49 g of diethyl 4-allylaminobenzylacetamidomalonate in the form of a beige solid which melts at 104-106° C. (Rf0.45 AcOEt 50/cyclohexane 50).

Source