Acetic Acid → Ethyl (4-oxo-2-sulfanylidene-1,2,3,4-tetrahydropyrimidin-5-yl)acetate

HRID 1485243Notes

Reaction equation

HRID 1485243 reaction equation
[O-]CC.[Na+].C([O:7][C:8](=O)[CH:9]([CH:16]=O)[CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])C.[NH2:19][C:20]([NH2:22])=[S:21].C(O)(=O)C>C(O)C>[O:7]=[C:8]1[C:9]([CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])=[CH:16][NH:22][C:20](=[S:21])[NH:19]1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 2315001,4-Diethyl 2-formylbutanedioateHCID 2723790ThioureaHCID 2723922Sodium ethoxide

Product 1

HCID 3659581Ethyl (4-oxo-2-sulfanylidene-1,2,3,4-tetrahydropyrimidin-5-yl)acetateYield 19%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

Sodium ethoxide (6.105 g, 89.71 mmol) was added to absolute ethanol (150 mL) under an atmosphere of nitrogen followed by diethyl-2-formylsuccinate (1105) (crude, 16.5 g) in absolute ethanol (30 mL) and thiourea (6.829 g, 89.71 mmol). The reaction mixture was heated at reflux for 1 hour then cooled to room temperature at which stirring was continued for 16 hours. The volatiles were evaporated under reduced pressure to give a brown oily solid. Cold aqueous acetic acid solution (15%; 120 mL) was added and the resulting mixture was sonicated and then stirred at 0° C. until all the residue was in suspension. The resulting precipitate was collected by filtration. The filter cake was washed with water (100 mL) and dried to give the title compound (I106) (6.31 g, 19% yield over 2 steps) as an off-white solid; 1H NMR (400 MHz, d6-DMSO) δ 7.44 (s, 1H), 4.05 (q, J=7.1 Hz, 2H), 3.28 (s, 2H), 1.17 (t, J=7.1 Hz, 3H). LCMS Method C: rt 2.92 min; m/z 213.0 [M−H]−.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 1 hour
  3. customThe volatiles were evaporated under reduced pressure
  4. customto give a brown oily solid
  5. customthe resulting mixture was sonicated
  6. stirringstirred at 0° C. until all the residue
  7. filtrationThe resulting precipitate was collected by filtration
  8. washThe filter cake was washed with water (100 mL)
  9. customdried

Sources & evidence

ORD record
ord-ea6efb2e585b4966a0fb146b218871ea
Source dataset
uspto-grants-2016_08
Patent number
US09421205B2

Reaction notes

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