4-Chloro-2-methylthiopyrimidine → 2-(Methylthio)-4-phenylpyrimidine

HRID 1795384Notes

Reaction equation

HRID 1795384 reaction equation
[C:1]1([Mg]Br)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Cl[C:10]1[CH:15]=[CH:14][N:13]=[C:12]([S:16][CH3:17])[N:11]=1>C1COCC1>[CH3:17][S:16][C:12]1[N:13]=[C:14]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH:15]=[CH:10][N:11]=1

Participants

4

Reactant 2

HCID 971134-Chloro-2-methylthiopyrimidineHCID 178418255HCID 178418255, compound

Product 1

HCID 8175782-(Methylthio)-4-phenylpyrimidineYield 53%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of phenylmagnesium bromide (1M in THF, 4.2 mL, 4.2 mmol) is added to a solution of 4-chloro-2-methylthio-pyrimidine (296 mg, 1.84 mmol) and Fe(acac)3 (32 mg, 0.09 mmol) in THF (10 mL) at −30° C. After stirring for 50 min at that temperature, the reaction is quenched with brine, the aqueous layer is extracted with Et2O, the combined organic phases are dried over Na2SO4 and evaporated, and the residue is purified by flash chromatography (hexane/ethyl acetate, 10:1). After eluting a first fraction containing biphenyl (90 mg), one obtains 2-methylthio-4-phenyl-pyrimidine as a pale yellow solid (197 mg, 53%). 1H NMR (300 MHz, CD2Cl2) δ 8.53 (d, 1H), 8.09–8.13 (m, 2H), 7.53–7.48 (m, 3H), 7.39 (d, 2H), 2.63 (s, 3H); 13C NMR (75 MHz, CD2Cl2) δ 173.0, 164.0, 158.0, 136.7, 131.1, 131.0, 129.2, 127.5, 127.4, 112.2, 14.3.

Workup

  1. customthe reaction is quenched with brine
  2. extractionthe aqueous layer is extracted with Et2O
  3. dry with materialthe combined organic phases are dried over Na2SO4
  4. customevaporated
  5. customthe residue is purified by flash chromatography (hexane/ethyl acetate, 10:1)
  6. washAfter eluting a first fraction
  7. additioncontaining biphenyl (90 mg), one

Sources & evidence

ORD record
ord-567d1ae6293045f08f29e40873572b19
Source dataset
uspto-grants-2006_04
Patent number
US07026478B2

Reaction notes

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