Pyridine → Chloroprallethrin

HRID 2230211Notes

Reaction equation

HRID 2230211 reaction equation
N1C=CC=CC=1.[CH3:7][C:8]1[C@@H:9]([OH:17])[CH2:10][C:11](=[O:16])[C:12]=1[CH2:13][C:14]#[CH:15].[Cl:18][C:19]([Cl:29])=[CH:20][C@@H:21]1[C@@H:23]([C:24](Cl)=[O:25])[C:22]1([CH3:28])[CH3:27].[Cl-].[NH4+]>C1(C)C=CC=CC=1>[Cl:18][C:19]([Cl:29])=[CH:20][C@@H:21]1[C@@H:23]([C:24]([O:17][C@H:9]2[CH2:10][C:11](=[O:16])[C:12]([CH2:13][C:14]#[CH:15])=[C:8]2[CH3:7])=[O:25])[C:22]1([CH3:27])[CH3:28]

Participants

6

Reactant 4

HCID 1049PyridineHCID 25517Ammonium ChlorideHCID 1569974-Hydroxy-3-methyl-2-(prop-2-yn-1-yl)cyclopent-2-en-1-oneHCID 6454308(1R,3S)-3-(2,2-Dichloroethenyl)-2,2-dimethylcyclopropanecarbonyl chloride

Product 1

HCID 57113547ChloroprallethrinYield 78.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

3.4 Grams of pyridine was added to a mixture of 5.0 g of (S)-2-methyl-4-oxo-3-(2-propynyl)-cyclopent-2-enyl alcohol, 8.0 g of (1R)-trans-3-(2, 2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid chloride and 50 ml of toluene under ice-cooling. The resulting mixture was allowed to react at room temperature for 12 hours. Thereafter, about 50 ml of a saturated aqueous ammonium chloride solution was added to the resultant reaction solution, which was then extracted with three 50-ml portions of diethyl ether. The combined diethyl ether layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was subjected to a silica gel column chromatography followed by recrystallization from a mixed solvent of hexane and ethyl acetate to obtain 8.9 g (yield: 78%) of (S)-2-methyl-4-oxo-3-(2-propynyl)-cyclopent-2-enyl (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (the present compound).

Workup

  1. temperaturecooling
  2. customto react at room temperature for 12 hours
  3. customreaction solution, which
  4. extractionwas then extracted with three 50-ml portions of diethyl ether
  5. washThe combined diethyl ether layer was washed with a saturated aqueous sodium chloride solution
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customfollowed by recrystallization from a mixed solvent of hexane and ethyl acetate

Sources & evidence

ORD record
ord-d848cd61a1d84daba8ce1e44fd1c0af7
Source dataset
uspto-grants-2002_07
Patent number
US06423745B1

Reaction notes

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