N,N-Dimethylaniline → Ethyl 4-chloro-6-methyl-2-(methylsulfanyl)pyrimidine-5-carboxylate

HRID 516029Notes

Reaction equation

HRID 516029 reaction equation
O[C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:6]([CH3:13])[N:5]=[C:4]([S:14][CH3:15])[N:3]=1.CN(C)C1C=CC=CC=1.P(Cl)(Cl)([Cl:27])=O>[Cl-].C([N+](CC)(CC)CC)C.C(#N)C>[Cl:27][C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:6]([CH3:13])[N:5]=[C:4]([S:14][CH3:15])[N:3]=1

Participants

6

Reactant 3

HCID 949N,N-DimethylanilineHCID 24813Phosphorus oxychlorideHCID 178469257HCID 178469257, compound

Product 1

HCID 22225416Ethyl 4-chloro-6-methyl-2-(methylsulfanyl)pyrimidine-5-carboxylateYield 83%

Reagents, catalysts & solvents 2

HCID 5946Tetraethylammonium ChlorideCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

Ethyl 4-hydroxy-6-methyl-2-(methylthio)pyrimidine-5-carboxylate (0.2 g, 0.876 mmol), tetraethylammonium chloride (0.145 g, 0.876 mmol), and N,N-dimethylaniline (0.112 mL, 0.876 mmol) were dispersed in acetonitrile (10 mL). The reaction mixture was stirred briefly followed by the addition of phosphorous oxychloride (0.204 mL, 2.190 mmol). The reaction was heated at 100° C. for 4 h. The solvent was subsequently removed in vacuo. The residue was poured onto ice to give an off-white oil, which was extracted with DCM (2×15 mL), and dried over anhydrous Na2SO4. The solvent was removed in vacuo to give the title compound as a yellowish-green oil (0.179 g, 83%). [M+H] calc'd for C9H11ClN2O2S, 247; found, 247.

Workup

  1. customThe solvent was subsequently removed in vacuo
  2. additionThe residue was poured onto ice
  3. customto give an off-white oil, which
  4. extractionwas extracted with DCM (2×15 mL)
  5. dry with materialdried over anhydrous Na2SO4
  6. customThe solvent was removed in vacuo

Sources & evidence

ORD record
ord-028e62c57f914eeba6e78e1238d6cc3d
Source dataset
uspto-grants-2015_08
Patent number
US09108970B2

Reaction notes

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