Hydrochloric Acid → HCID 14718729, compound

HRID 1085700Notes

Reaction equation

HRID 1085700 reaction equation
[Mg].II.Br[C:5]1[CH:6]=[N:7][C:8]([C:11]([CH3:14])([CH3:13])[CH3:12])=[N:9][CH:10]=1.CI.N1C=CC=NC=1.[C:23](OCC)(=[O:29])[C:24]([O:26][CH2:27][CH3:28])=[O:25].Cl>O1CCCC1>[O:29]=[C:23]([C:5]1[CH:6]=[N:7][C:8]([C:11]([CH3:14])([CH3:13])[CH3:12])=[N:9][CH:10]=1)[C:24]([O:26][CH2:27][CH3:28])=[O:25]

Participants

9

Reactant 7

HCID 313Hydrochloric AcidHCID 807IodineHCID 6328Methyl iodideHCID 7268Diethyl OxalateHCID 9260PyrimidineHCID 5462224MagnesiumHCID 135328985-Bromo-2-tert-butylpyrimidine

Product 1

HCID 14718729HCID 14718729, compoundYield 55.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

Magnesium turnings (1.9 g), a catalytic amount of iodine and dry tetrahydrofuran (50 cm3) were placed in a round-bottomed flask under an atmosphere of dry nitrogen. A portion of a solution of 5-bromo-2-(1,1-dimethylethyl)pyrimidine (15.2 g) in dry tetrahydrofuran (50 cm3) was added to the reaction vessel and the Grignard reaction was initiated by the addition of a small portion of methyl iodide, followed by heating the reaction contents to the reflux temperature. The remainder of the pyrimidine solution was added at such a rate so as to maintain reflux, and on completion of the addition and cessation of reaction, the so formed Grignard reagent was added to a solution of diethyl oxalate (20.4 g) in dry tetrahydrofuran, whilst the reaction temperature was maintained between -10° C. and -15° C. After the addition was complete, the reaction mixture was allowed to warm to the ambient temperature, at which point it was allowed to stir for 16 hours. Dilute aqueous hydrochloric acid was added to the reaction mixture which was then extracted into dichloromethane. The combined organic extracts were washed with water, and brine, and dried over anhydrous magnesium sulphate. Evaporation of the solvent under reduced pressure, and short-path distillation of the residue using a Kugelrohr apparatus gave ethyl 2-oxo-2-[2-(1,1-dimethylethyl)-pyrimidin-5-yl]-acetate (9.3 g).

Workup

  1. customthe Grignard reaction
  2. temperatureby heating
  3. customthe reaction contents to the reflux temperature
  4. temperatureto maintain
  5. temperaturereflux
  6. additionon completion of the addition and cessation of reaction
  7. temperaturewas maintained between -10° C. and -15° C
  8. additionAfter the addition
  9. extractionwas then extracted into dichloromethane
  10. washThe combined organic extracts were washed with water, and brine
  11. dry with materialdried over anhydrous magnesium sulphate
  12. customEvaporation of the solvent
  13. distillationunder reduced pressure, and short-path distillation of the residue

Sources & evidence

ORD record
ord-f0e77b4e8df544ccaf5df3f961b0ea6f
Source dataset
uspto-grants-1991_04
Patent number
US05010200

Reaction notes

Loading…