2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 2,6-Dichloro-5-methoxy-4-allyl pyrimidine

HRID 332919

Reaction equation

HRID 332919 reaction equation
[Cl:1][C:2]1[NH:3][C:4](Cl)([CH2:10][CH:11]=[CH2:12])[C:5]([O:8][CH3:9])=[CH:6][N:7]=1.[Cl:14]C1N=CC(OC)=C(Cl)N=1.C([Mg]Br)C=C.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>C1COCC1>[Cl:1][C:2]1[N:3]=[C:4]([CH2:10][CH:11]=[CH2:12])[C:5]([O:8][CH3:9])=[C:6]([Cl:14])[N:7]=1

Participants

6

Reactant 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 6014012,4-Dichloro-5-methoxypyrimidine2×HCID 178439543HCID 178439543, compound2×HCID 178455850HCID 178455850, compound

Product 1

HCID 866893282,6-Dichloro-5-methoxy-4-allyl pyrimidineYield 67%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

2,6-Dichloro-5-methoxy-6-allyl pyrimidine may be prepared using 2,6-dichloro-5-methoxy pyrimidine, which is commercially available. 2,6-Dichloro-5-methoxy pyrimidine (3.0 g, 17 mmol) was dissolved in THF (30 mL) and treated in portions with allyl magnesium bromide (17 mL of 1M allyl magnesium bromide in diethyl ether, 17 mmol). The resulting reaction was exothermic. External cooling was used to keep the temperature of the mixture below 30° C. After 20 minutes, the mixture was subjected to HPLC and GC-MS. After 45 minutes, the mixture was cooled in ice/salt and the reaction quenched with saturated ammonium chloride (30 mL) then diluted with ethyl acetate (75 mL). The organic phase was washed with saturated sodium chloride (30 mL), dried, and evaporated. The residue was dissolved in 1,4-dioxane (50 mL), treated with DDQ (3.9 g, 17 mmol), and stirred for 20 h. GC-MS showed presence of 2,6-dichloro-5-methoxy-6-allyl pyrimidine (having molar weight of 218 g/mol). The residue was washed in water and ethyl acetate and purified by column chromatography using silica with ethyl acetate and hexane. This provided the title compound (2.5 g, 67% yield): mp 61-62° C. 1H NMR (400 MHz, CDCl3) δ 6.07-5.94 (m, 1H), 5.26-5.16 (m, 2H), 3.94-3.89 (s, 3H), 3.65-3.56 (m, 2H)); EIMS m/z 218.

Workup

  1. customThe resulting reaction
  2. temperatureExternal cooling
  3. customthe temperature of the mixture below 30° C
  4. waitAfter 45 minutes
  5. temperaturethe mixture was cooled in ice/salt
  6. customthe reaction quenched with saturated ammonium chloride (30 mL)
  7. additionthen diluted with ethyl acetate (75 mL)
  8. washThe organic phase was washed with saturated sodium chloride (30 mL)
  9. customdried
  10. customevaporated
  11. dissolutionThe residue was dissolved in 1,4-dioxane (50 mL)
  12. washThe residue was washed in water
  13. customethyl acetate and purified by column chromatography

Sources & evidence

ORD record
ord-c0b546235c334a79bf831c2c8d692894
Source dataset
uspto-grants-2014_11
Patent number
US08877925B2

Linked notes

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