Diethyl Ether → 2,5-Dichloro-4-methylpyrimidine

HRID 2174985Notes

Reaction equation

HRID 2174985 reaction equation
[Cl:1][C:2]1[N:7]=[C:6](Cl)[C:5]([Cl:9])=[CH:4][N:3]=1.C[Mg+].[Br-].[CH3:13]COCC>C1COCC1.CN1C(=O)CCC1>[Cl:1][C:2]1[N:7]=[C:6]([CH3:13])[C:5]([Cl:9])=[CH:4][N:3]=1

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 2372592,4,5-TrichloropyrimidineHCID 178418689HCID 178418689, compound

Product 1

HCID 212786212,5-Dichloro-4-methylpyrimidineYield 65%

Reagents, catalysts & solvents 1

HCID 22156051tetrahydrofuran N-methylpyrrolidinoneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 2,4,5-trichloropyrimidine (2.52 g, 13.74 mmol) in THF/NMP (86 mL/6 mL) was added Fe(acac)3 (485 mg, 1.37) and the mixture was cooled to 0° C. 3.0 M MeMgBr in Et2O (6.87 mL, 20.61 mmol) was added dropwise. After 30 min at 0° C., the reaction was complete and quenched with saturated aqueous NH4Cl solution. Et2O was added and the layers were separated and the aqueous layer was further extracted with several portions of Et2O. The combined organic extracts were dried over Na2SO4, filtered and concentrated in vacuo. Chromatography (Hex to 10% EtOAc/Hex) gave the desired product as a white solid (1.45 g, 65%). 1H NMR (500 MHz, CDCl3): 8.47 (s, 1H), 2.61 (s, 3H).

Workup

  1. customquenched with saturated aqueous NH4Cl solution
  2. additionEt2O was added
  3. customthe layers were separated
  4. extractionthe aqueous layer was further extracted with several portions of Et2O
  5. dry with materialThe combined organic extracts were dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-43c0126187064968820494b8fbd37e19
Source dataset
uspto-grants-2015_06
Patent number
US09062044B2

Reaction notes

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