Diethyl 5-hydantoylphosphonate → Ethyl 4-[3-[(2,4-dioxoimidazolidin-5-ylidene)methyl]-4-nitrophenoxy]butanoate

HRID 867472Notes

Reaction equation

HRID 867472 reaction equation
[Na].[O:2]=[C:3]1[NH:7][C:6](=[O:8])[CH:5](P(OCC)(=O)OCC)[NH:4]1.[CH:17]([C:19]1[CH:20]=[C:21]([CH:31]=[CH:32][C:33]=1[N+:34]([O-:36])=[O:35])[O:22][CH2:23][CH2:24][CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27])=O>C(O)C>[O:2]=[C:3]1[NH:7][C:6](=[O:8])[C:5](=[CH:17][C:19]2[CH:20]=[C:21]([CH:31]=[CH:32][C:33]=2[N+:34]([O-:36])=[O:35])[O:22][CH2:23][CH2:24][CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27])[NH:4]1

Participants

5

Reactant 3

HCID 3516088Diethyl 5-hydantoylphosphonateHCID 5360545SodiumHCID 10588876Ethyl 4-((3-formyl-4-nitrophenyl)oxy)butyrate

Product 1

HCID 54441560Ethyl 4-[3-[(2,4-dioxoimidazolidin-5-ylidene)methyl]-4-nitrophenoxy]butanoateYield 95%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

Sodium (4.92 g, 0.21 g atom) was dissolved in absolute ethanol (600 mL) and diethyl 2,4-dioxoimidazolidine-5-phosphonate (50.5 g, 0.21 mole) added. After 10 minutes, a solution of ethyl 4-(3-formyl-4-nitrophenoxy)butanoate (50.0 g, 0.18 mole) in ethanol (100 mL) was added in one portion. The mixture was stirred for 2 hours, concentrated in vacuo to about 250 mL and diluted with water. After 20 minutes the precipitate was filtered off. Two further crops were subsequently collected from mother liquors. Combined solids were dried in vacuo over P2O5 to afford ethyl 4-[3-[(2,4-dioxoimidazolidin-5-ylidene)methyl]-4-nitrophenoxy]butanoate (61.3 g, 95%) which by NMR was a 4:1 mixture of geometrical isomers. An analytical sample of the major isomer was obtained by crystallization from aqueous ethanol and had m.p. 131°-134° C.

Workup

  1. concentrationconcentrated in vacuo to about 250 mL
  2. additiondiluted with water
  3. filtrationAfter 20 minutes the precipitate was filtered off
  4. customTwo further crops were subsequently collected from mother liquors
  5. dry with materialwere dried in vacuo over P2O5

Sources & evidence

ORD record
ord-cc3bc41383094f30b6cc60090adf1ee0
Source dataset
uspto-grants-1988_10
Patent number
US04775674

Reaction notes

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