Acetic Acid → HCID 12535871, compound

HRID 437448Notes

Reaction equation

HRID 437448 reaction equation
C=O.[C:3]([BH3-])#[N:4].[Na+].[O:7]=[C:8]1[NH:13][C:12]([C:14]2[CH:19]=[C:18](N)[CH:17]=[CH:16][C:15]=2[O:21][CH2:22][CH3:23])=[N:11][CH:10]=[C:9]1[C:24]([O:26]CC)=[O:25].[C:29](O)(=O)C>O.C(#N)C.C(OCC)C>[O:7]=[C:8]1[NH:13][C:12]([C:14]2[CH:19]=[C:18]([N:4]([CH3:3])[CH3:29])[CH:17]=[CH:16][C:15]=2[O:21][CH2:22][CH3:23])=[N:11][CH:10]=[C:9]1[C:24]([OH:26])=[O:25]

Participants

8

Reactant 4

HCID 176Acetic Acid2×HCID 712FormaldehydeHCID 5003444Sodium cyanoborohydrideHCID 12535828HCID 12535828, compound

Product 1

HCID 12535871HCID 12535871, compoundYield 29%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolvent

Procedure

A solution (1.9 ml.) of 37% formaldehyde (23.8 mmoles) in water followed by sodium cyanoborohydride (450 mg., 7.15 mmoles) were added to a stirred solution of ethyl 1,6-dihydro-6-oxo-2-(5-amino-2-ethoxyphenyl)pyrimidine-5-carboxylate (720 mg., 2.38 mmoles) in acetonitrile (14 ml.). Glacial acetic acid (0.24 ml.) was then added over a period of one minute. The mixture was stirred at room temperature for 2 hours. Additional glacial acetic acid (0.24 ml.) was added and stirring was continued for an extra 0.5 hour. The mixture was treated with diethyl ether (35 ml.). The organic layer was washed with 10% aqueous sodium bicarbonate (3 × 10 ml.) followed by brine (30 ml.) and dried (sodium sulfate). The solvent was removed and a solution of the residue in acetonitrile-diethyl ether was extracted with 1 N sodium hydroxide (3 × 20 ml.). The aqueous extract was acidified with glacial acetic acid to pH 6. The precipitate was collected and recrystallized from acetonitrile to give the title compound (210 mg., 29%), m.p. 187°-196°. Recrystallization from benzene-Skellysolve B gave analytical material, m.p. 195°-198°.

Workup

  1. stirringstirring
  2. waitwas continued for an extra 0.5 hour
  3. washThe organic layer was washed with 10% aqueous sodium bicarbonate (3 × 10 ml.)
  4. dry with materialdried (sodium sulfate)
  5. customThe solvent was removed
  6. extractiona solution of the residue in acetonitrile-diethyl ether was extracted with 1 N sodium hydroxide (3 × 20 ml.)
  7. extractionThe aqueous extract
  8. customThe precipitate was collected
  9. customrecrystallized from acetonitrile

Sources & evidence

ORD record
ord-93daea7cb90042509499ed503232ab5e
Source dataset
uspto-grants-1977_06
Patent number
US04031093

Reaction notes

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