Acetonitrile → (4,6-Dichloropyrimidin-5-yl)acetaldehyde

HRID 922334Notes

Reaction equation

HRID 922334 reaction equation
S1CCS[CH:2]1[CH2:6][C:7]1[C:8]([Cl:14])=[N:9][CH:10]=[N:11][C:12]=1[Cl:13].C(#N)C.C(=O)([O-])[O-:19].[Ca+2]>[Hg](Cl)Cl.O>[Cl:14][C:8]1[C:7]([CH2:6][CH:2]=[O:19])=[C:12]([Cl:13])[N:11]=[CH:10][N:9]=1

Participants

6

Reactant 3

HCID 6342AcetonitrileHCID 10112Calcium CarbonateHCID 118589648HCID 118589648, compound

Product 1

HCID 13989292(4,6-Dichloropyrimidin-5-yl)acetaldehydeYield 87%

Reagents, catalysts & solvents 2

HCID 24085Mercuric ChlorideCatalystHCID 962WaterSolvent

Procedure

5-[(1,3-dithiolan-2-yl)methyl]-4,6-dichloropyrimidine (compound of the formula IV-1, 13.4 g, 0.05 mol) was added to 200 mL of a 4:1 mixture of acetonitrile and water, and mercury dichloride (27.1 g, 0.1 mol) and calcium carbonate (10 g, 0.1 mol) were then further added with stirring. After 6 hours of reaction at the room temperature, suction filtration was carried out. The solid was washed with acetonitrile and then the combined filtrate was subjected to solvent removal, followed by the addition of 200 mL of dichloromethane. The organic phase was then washed with an aqueous solution saturated with sodium bicarbonate, dried and subjected to solvent removal, resulting in a yellow solid. The solid was then recrystallized in ethyl acetate and petroleum ether (1:1) in order to obtain a yellowish solid of 8.3 g with a yield of 87%. 1HNMR (400 MHz, CDCl3) δ: 9.80 (s, 1H), 8.74 (s, 1H), 4.14 (s, 2H).

Workup

  1. additionwere then further added
  2. customAfter 6 hours of reaction
  3. filtrationat the room temperature, suction filtration
  4. washThe solid was washed with acetonitrile
  5. customthe combined filtrate was subjected to solvent removal
  6. additionfollowed by the addition of 200 mL of dichloromethane
  7. washThe organic phase was then washed with an aqueous solution saturated with sodium bicarbonate
  8. customdried
  9. customsubjected to solvent removal
  10. customresulting in a yellow solid
  11. customThe solid was then recrystallized in ethyl acetate
  12. custompetroleum ether (1:1) in order to obtain a yellowish solid of 8.3 g with a yield of 87%

Sources & evidence

ORD record
ord-2aed040f1ec1462fb178e41b3688f61a
Source dataset
uspto-grants-2016_03
Patent number
US09278939B2

Reaction notes

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