Methanol → (2,3,5,6-tetrafluoro-4-methylphenyl)methyl (1R)-trans-3-formyl-2,2-dimethylcyclopropanecarboxylate

HRID 1636448Notes

Reaction equation

HRID 1636448 reaction equation
[CH3:1][C:2]1([CH3:24])[C@H:4]([CH:5]=C(C)C)[C@H:3]1[C:9]([O:11][CH2:12][C:13]1[C:18]([F:19])=[C:17]([F:20])[C:16]([CH3:21])=[C:15]([F:22])[C:14]=1[F:23])=[O:10].CO.O=O.[O:29]=[O+][O-]>O.C(OCC)(=O)C>[CH:5]([C@@H:4]1[C@@H:3]([C:9]([O:11][CH2:12][C:13]2[C:18]([F:19])=[C:17]([F:20])[C:16]([CH3:21])=[C:15]([F:22])[C:14]=2[F:23])=[O:10])[C:2]1([CH3:24])[CH3:1])=[O:29]

Participants

7

Reactant 4

HCID 887MethanolHCID 977OxygenHCID 24823OzoneHCID 11580987(2,3,5,6-tetrafluoro-4-methylphenyl)methyl(1R)-trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate

Product 1

HCID 15451879(2,3,5,6-tetrafluoro-4-methylphenyl)methyl (1R)-trans-3-formyl-2,2-dimethylcyclopropanecarboxylateYield 82%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

A mixture of 1.27 g of (2,3,5,6-tetrafluoro-4-methylphenyl)methyl (1R)-trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate, 20 ml of methanol and 20 ml of ethyl acetate was cooled to -78° C. Oxygen-containing ozone was bubbled into the mixture while stirring until the reaction mixture was colored blue. Then, nitrogen gas was bubbled into the blue reaction mixture to remove the excess ozone. Thereafter, 5 ml of dimethyl sulfide was added thereto. The resulting mixture was heated to room temperature. The reaction mixture, after having been allowed to stand for one day, was concentrated under reduced pressure. 20 Milliliters of acetone, 2 ml of water and 0.2 g of p-toluenesulfonic acid monohydrate were added to the resultant residue. The resulting reaction mixture, after having been allowed to stand at room temperature for 2 hours, was poured into water and extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resultant residue was purified by a silica gel column chromatography (eluent: hexane/ethyl acetate=10/1) to obtain 0.98 g (yield: 82%) of (2,3,5,6-tetrafluoro-4-methylphenyl)methyl (1R)-trans-3-formyl-2,2-dimethyl-cyclopropanecarboxylate, m.p. 43.2° C.

Workup

  1. customwas bubbled into the mixture
  2. customThen, nitrogen gas was bubbled into the blue reaction mixture
  3. customto remove the excess ozone
  4. additionThereafter, 5 ml of dimethyl sulfide was added
  5. temperatureThe resulting mixture was heated to room temperature
  6. concentrationwas concentrated under reduced pressure
  7. addition20 Milliliters of acetone, 2 ml of water and 0.2 g of p-toluenesulfonic acid monohydrate were added to the resultant residue
  8. customThe resulting reaction mixture
  9. waitto stand at room temperature for 2 hours
  10. extractionextracted with diethyl ether
  11. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  12. concentrationconcentrated under reduced pressure
  13. customThe resultant residue was purified by a silica gel column chromatography (eluent: hexane/ethyl acetate=10/1)

Sources & evidence

ORD record
ord-3c4425e1768b48368449e16399fa1190
Source dataset
uspto-grants-2000_03
Patent number
US06034128

Reaction notes

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