p-Aminoacetophenone → N-[4-(1-hydroxyiminoethyl)phenyl]-N'-(1-methoxycarbonyl-2-carbamoylethyl)urea

HRID 247223Notes

Reaction equation

HRID 247223 reaction equation
[CH3:1][C:2]([C:4]1[CH:9]=[CH:8][C:7]([NH2:10])=[CH:6][CH:5]=1)=O.[N-:11]=[C:12]=[O:13].[CH3:14][O:15][C:16](=[O:23])[C@H:17]([CH2:19][C:20](=[O:22])[NH2:21])N.Cl.[NH2:25][OH:26].C(OC)(OC)OC>C1COCC1.N1C=CC=CC=1>[OH:26][N:25]=[C:2]([C:4]1[CH:9]=[CH:8][C:7]([NH:10][C:12]([NH:11][CH:17]([C:16]([O:15][CH3:14])=[O:23])[CH2:19][C:20](=[O:22])[NH2:21])=[O:13])=[CH:6][CH:5]=1)[CH3:1]

Participants

7

Reactant 4

HCID 7468p-AminoacetophenoneHCID 9005Trimethyl orthoformateHCID 443297Hydroxyamine hydrochlorideHCID 86741878Asparagine methyl ester isocyanate

Product 1

HCID 86741883N-[4-(1-hydroxyiminoethyl)phenyl]-N'-(1-methoxycarbonyl-2-carbamoylethyl)urea

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 0.02 mol 4-aminoacetophenone in 40 mL THF is added dropwise to a solution of 0.02 mol of asparagine methyl ester isocyanate and 5 mL pyridine in 40 mL THF, and the reaction mixture is stirred for 3 hours. The solvent is then removed by rotary evaporator. The residue is dispersed in 50 mL CH3OH, and 0.022 mol hydroxylamine hydrochloride and 0.06 mol trimethyl orthoformate are added. The reaction mixture is heated to reflux for 1 hour. The solvent is removed by rotary evaporator. Addition of water to the residue results in precipitation of N-[4-(1-hydroxyiminoethyl)phenyl]-N'-(1-methoxycarbonyl-2-carbamoylethyl)urea, which is then treated with NaOCH3 to adjust the pH to 10. The solution is heated to reflux for 2.5 hours, and the solvent is removed under vacuum. The residue is washed with cold water to yield the crude 3-[4-(1-hydroxyiminoethyl)phenyl]-5-carbamoylmethylhydantoin. The hydantoin is purified by recrystallization from CH3OH:H2O.

Workup

  1. customThe solvent is then removed by rotary evaporator
  2. additionThe residue is dispersed in 50 mL CH3OH
  3. temperatureThe reaction mixture is heated
  4. temperatureto reflux for 1 hour
  5. customThe solvent is removed by rotary evaporator
  6. additionAddition of water to the residue

Sources & evidence

ORD record
ord-c915c5b4fa274dad8fd9f75b62114126
Source dataset
uspto-grants-1987_11
Patent number
US04705864

Reaction notes

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