Triethyl Phosphate → (rac)-Allyl 4-(4-cyano-2-nitrophenyl)-6-methyl-2-oxo-1-[3-(trifluoromethyl)phenyl]-1,2,3,4-tetrahydropyrimidine-5-carboxylate

HRID 2361903Notes

Reaction equation

HRID 2361903 reaction equation
[C:1]([O:7][CH2:8][CH:9]=[CH2:10])(=[O:6])[CH2:2][C:3]([CH3:5])=O.[C:11]([C:13]1[CH:20]=[CH:19][C:16]([CH:17]=O)=[C:15]([N+:21]([O-:23])=[O:22])[CH:14]=1)#[N:12].[F:24][C:25]([F:37])([F:36])[C:26]1[CH:27]=[C:28]([NH:32][C:33]([NH2:35])=[O:34])[CH:29]=[CH:30][CH:31]=1.P(OCC)(OCC)(OCC)=O>C1COCC1.C(OCC)(=O)C.C(OCC)C>[C:11]([C:13]1[CH:20]=[CH:19][C:16]([CH:17]2[C:2]([C:1]([O:7][CH2:8][CH:9]=[CH2:10])=[O:6])=[C:3]([CH3:5])[N:32]([C:28]3[CH:29]=[CH:30][CH:31]=[C:26]([C:25]([F:36])([F:37])[F:24])[CH:27]=3)[C:33](=[O:34])[NH:35]2)=[C:15]([N+:21]([O-:23])=[O:22])[CH:14]=1)#[N:12]

Participants

8

Reactant 4

HCID 6535Triethyl PhosphateHCID 25712(3-Trifluoromethylphenyl)ureaHCID 70701Allyl acetoacetateHCID 132385504-Formyl-3-nitrobenzonitrile

Product 1

HCID 58133797(rac)-Allyl 4-(4-cyano-2-nitrophenyl)-6-methyl-2-oxo-1-[3-(trifluoromethyl)phenyl]-1,2,3,4-tetrahydropyrimidine-5-carboxylate

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

The reaction was carried out under argon. At RT, allyl acetoacetate (5.94 g, 41.5 mmol; 1.0 eq.) was initially charged in THF (117 ml). 4-Cyano-2-nitrobenzaldehyde (10.45 g, 70% pure, 41.5 mmol; 1.0 eq.), 1-[3-(trifluoromethyl)phenyl]urea (8.48 g, 41.5 mmol) and triethyl phosphate (17.7 g) were then added. The mixture was stirred under reflux for 16 h. For work-up, ice-water was initially added, and the mixture was then taken up in ethyl acetate (400 ml). The organic phase was dried over solid sodium sulfate, filtered and concentrated under reduced pressure. The crude product was recrystallized from hot water/isopropanol (2:1, ˜400 ml). The solid obtained was stirred in diethyl ether (60 ml), once more filtered off with suction, washed with a little diethyl ether and dried under high vacuum. The title compound was obtained as a solid (16.63 g, 82% of theory).

Workup

  1. temperatureunder reflux for 16 h
  2. dry with materialThe organic phase was dried over solid sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated under reduced pressure
  5. customThe crude product was recrystallized from hot water/isopropanol (2:1, ˜400 ml)
  6. customThe solid obtained
  7. filtrationonce more filtered off with suction
  8. washwashed with a little diethyl ether
  9. customdried under high vacuum

Sources & evidence

ORD record
ord-d74084b424bc4229bf4bd88c78137355
Source dataset
uspto-grants-2014_04
Patent number
US08691817B2

Reaction notes

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