Water → HCID 54264222, compound

HRID 275646Notes

Reaction equation

HRID 275646 reaction equation
[NH2:1][C:2]1[CH:23]=[CH:22][C:5]([CH2:6][CH2:7][C:8]([NH:10][CH:11]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:12]([O:14][CH2:15][CH3:16])=[O:13])=[O:9])=[CH:4][CH:3]=1.[CH2:24](Br)[CH:25]=[CH2:26].C(N([CH2:33][CH3:34])CC)C.O.[CH3:36]N(C=O)C>>[CH2:24]([N:1]([CH2:36][CH:33]=[CH2:34])[C:2]1[CH:3]=[CH:4][C:5]([CH2:6][CH2:7][C:8]([NH:10][CH:11]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:12]([O:14][CH2:15][CH3:16])=[O:13])=[O:9])=[CH:22][CH:23]=1)[CH:25]=[CH2:26].[CH2:26]([NH:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:6][CH2:7][C:8]([NH:10][CH:11]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:12]([O:14][CH2:15][CH3:16])=[O:13])=[O:9])=[CH:22][CH:23]=1)[CH:25]=[CH2:24]

Participants

7

Reactant 5

HCID 962WaterHCID 6228DimethylformamideHCID 7841Allyl bromide2×HCID 8471Triethylamine2×HCID 53821646HCID 53821646, compound

Product 2

HCID 54264222HCID 54264222, compoundHCID 54416959HCID 54416959, compound

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).

Workup

  1. customare placed in a three-necked flask
  2. customwhich is surmounted with a dropping funnel
  3. temperaturemaintained under a nitrogen atmosphere
  4. stirringAfter stirring for 19 h
  5. stirringthe mixture is stirred for 26 h
  6. extractionthis mixture is extracted with 1 l of ethyl acetate
  7. customThe aqueous phase is separated off after settling
  8. washwashed with 2 times 500 ml of ethyl acetate
  9. washwashed with 500 ml of distilled water
  10. customseparated off
  11. dry with materialdried over magnesium sulphate
  12. filtrationfiltered
  13. concentrationconcentrated to dryness in order
  14. customto yield a chestnut oil
  15. customthis oil is purified by flash chromatography (eluant, CH2Cl290/AcOEt 10) in order

Sources & evidence

ORD record
ord-86df17c6bb4741a88a27b74fcbf1ebf9
Source dataset
uspto-grants-2002_03
Patent number
US06352839B1

Reaction notes

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