Phosphorus oxychloride → Ethyl 4-chloro-6-methyl-2-(methylsulfanyl)pyrimidine-5-carboxylate

HRID 1893888Notes

Reaction equation

HRID 1893888 reaction equation
[CH3:1][C:2]1[N:3]=[C:4]([S:14][CH3:15])[NH:5][C:6](=O)[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9].P(Cl)(Cl)([Cl:18])=O>C(OC(=O)C)C>[Cl:18][C:6]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:2]([CH3:1])[N:3]=[C:4]([S:14][CH3:15])[N:5]=1

Participants

4

Reactant 2

HCID 24813Phosphorus oxychloride2×HCID 135504073Ethyl 4-methyl-2-(methylthio)-6-oxo-1,6-dihydropyrimidine-5-carboxylate

Product 1

HCID 22225416Ethyl 4-chloro-6-methyl-2-(methylsulfanyl)pyrimidine-5-carboxylate

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

A solution of ethyl 4-methyl-2-(methylthio)-6-oxo-1,6-dihydropyrimidine-5-carboxylate (60 g, 0.26 mole) and phosphorous oxychloride (POCl3, 320 mL) was heated under reflux for 4 to 5 h (monitor reaction by TLC using 30% ethylacetate and hexanes). After completion of reaction, phosphorous oxychloride was removed on a rotary evaporator. The residue was poured on to ice water and extracted with ethylacetate several times. The combined organic layers were evaporated, on a rotary evaporator, to give crude ethyl 4-chloro-6-methyl-2-(methylthio)pyrimidine-5-carboxylate (65 g). This compound was used without purification.

Workup

  1. temperatureunder reflux for 4 to 5 h (
  2. customwas removed on a rotary evaporator
  3. additionThe residue was poured on to ice water
  4. extractionextracted with ethylacetate several times
  5. customThe combined organic layers were evaporated, on a rotary evaporator

Sources & evidence

ORD record
ord-55d3a61abffb47aa84c0cd250a251e62
Source dataset
uspto-grants-2013_08
Patent number
US08513266B2

Reaction notes

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