2,4-Dichloropyrimidine → 4-(2-thienyl)pyrimidine

HRID 2377781Notes

Reaction equation

HRID 2377781 reaction equation
Cl[C:2]1[N:7]=[C:6](Cl)[CH:5]=[CH:4][N:3]=1.[Br-].O1CCOC1[C:15]1[S:19][C:18]([Zn+])=[CH:17][CH:16]=1>O1CCCC1.CCOCC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[S:19]1[CH:15]=[CH:16][CH:17]=[C:18]1[C:6]1[CH:5]=[CH:4][N:3]=[CH:2][N:7]=1

Participants

6

Reactant 2

HCID 775312,4-DichloropyrimidineHCID 178419758HCID 178419758, compound

Product 1

HCID 8189684-(2-thienyl)pyrimidine

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
70 °C

Procedure

To a degassed 0.50 M solution of 2,4-dichloropyrimidine (1.0 eq.) and 5-(1,3-dioxolan-2-yl)-2-thienylzinc bromide 31 (1.0 eq.) in tetrahydrofuran was added tetrakis(triphenylphosphine)palladium(0) (0.050 eq.). The mixture was stirred for 16 h at 70° C. and then returned to ambient temperature and diluted with ether. The solution was washed sequentially with a 0.5 M aqueous pH 9 solution of EDTA and brine. The organic phase was dried over sodium sulfate, filtered, and concentrated. The crude material was purified by flash chromatography over silica gel (1:1:1 hexanes:ethyl acetate:dichloromethane) to give compound 32. ES/MS m/z 269 (MH+), C11H9ClN2O2S=269 g/mol.

Workup

  1. customreturned to ambient temperature
  2. washThe solution was washed sequentially with a 0.5 M aqueous pH 9 solution of EDTA and brine
  3. dry with materialThe organic phase was dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe crude material was purified by flash chromatography over silica gel (1:1:1 hexanes:ethyl acetate:dichloromethane)

Sources & evidence

ORD record
ord-1d943bf187684ce6a13849cd14601d9d
Source dataset
uspto-grants-2008_12
Patent number
US07470701B2

Reaction notes

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