Carbon Dioxide → 4,6-Dichloro-2-(methylthio)pyrimidine-5-carboxylic acid

HRID 917633Notes

Reaction equation

HRID 917633 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[Cl:13][C:14]1[CH:19]=[C:18]([Cl:20])[N:17]=[C:16]([S:21][CH3:22])[N:15]=1.[C:23](=[O:25])=[O:24].Cl>O1CCCC1.CCCCCC.O>[Cl:13][C:14]1[C:19]([C:23]([OH:25])=[O:24])=[C:18]([Cl:20])[N:17]=[C:16]([S:21][CH3:22])[N:15]=1

Participants

9

Reactant 5

HCID 280Carbon DioxideHCID 313Hydrochloric AcidHCID 7912DiisopropylamineHCID 805314,6-Dichloro-2-(methylthio)pyrimidineHCID 178418339Butyllithium

Product 1

HCID 220535774,6-Dichloro-2-(methylthio)pyrimidine-5-carboxylic acid

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

To a solution of diisopropylamine 11.93 g in tetrahydrofuran 350 ml is dropped a 1.6M solution of n-butyl lithium in hexane 73.7 ml over a period of 20 minutes on dry ice-acetone bath, and the mixture is stirred for 30 minutes. Thereto is added 4,6-dichloro-2-methylthiopyrimidine 10.00 g in tetrahydrofuran 50 ml over a period of 1 hour on a dry ice-acetone bath, followed by further one hour agitation. The reaction mixture is poured into dry ice and the mixture is stirred for 1.5 hours at room temperature. The reaction mixture is made acidic with 10% hydrochloric acid, diluted with water and extracted with ethyl acetate. The organic layer is washed, dried and condensed in vacuo. The resulting solid is triturated with hexane to give 4,6-dichloro-5-carboxy-2-methylthiopyrimidine as a brown crystalline powder, 10.42 g. mp 151-158° C. (decomposition)

Workup

  1. waitfollowed by further one hour
  2. stirringthe mixture is stirred for 1.5 hours at room temperature
  3. extractionextracted with ethyl acetate
  4. washThe organic layer is washed
  5. customdried
  6. customcondensed in vacuo
  7. customThe resulting solid is triturated with hexane

Sources & evidence

ORD record
ord-ad12a8676be74174b41f0e712d704e83
Source dataset
uspto-grants-2007_09
Patent number
US07273868B2

Reaction notes

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