Dimethyl Sulfide → (1R,cis)-2-[2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropyl]ethylidene diacetate

HRID 27672Notes

Reaction equation

HRID 27672 reaction equation
[C:1]([O:4][CH:5](C(=O)C)[CH2:6][CH:7]1[C:9]([CH3:11])([CH3:10])[CH:8]1[CH:12]=[C:13]([Cl:15])[Cl:14])(=[O:3])[CH3:2].C(Cl)(Cl)Cl.ClC1C=CC=[C:26]([C:30]([O:32]O)=[O:31])C=1.CSC>ClCCl>[C:30]([O:32][CH:5]([O:4][C:1](=[O:3])[CH3:2])[CH2:6][C@H:7]1[C:9]([CH3:10])([CH3:11])[C@H:8]1[CH:12]=[C:13]([Cl:14])[Cl:15])(=[O:31])[CH3:26]

Participants

6

Reactant 4

HCID 1068Dimethyl SulfideHCID 6212ChloroformHCID 70297m-Chloroperbenzoic acid2×HCID 54126646HCID 54126646, compound

Product 1

HCID 53872629(1R,cis)-2-[2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropyl]ethylidene diacetateYield 63%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

The contents of a 50-ml flask charged with 1-[2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropyl]-3-oxo-2-butyl acetate prepared as in Embodiment VI above (11.9 mmol, 100% (1R,cis) both spatial configurations around C--C(O)CH3 present), chloroform (10 ml) and 3-chloroperbenzoic acid (26 mmol) were stirred magnetically for five hours at 20° C. Then, another quantity of 3-chloroperbenzoic acid (6 mmol) was added and stirring was continued for 16 hours. The reaction mixture obtained was mixed with dimethyl sulphide (2 ml), keeping the temperature at 20° C., stirring was continued for 15 minutes, dichloromethane (30 ml) was added, the suspended material was filtered off, the filtrate was washed with two 20-ml portions of a saturated aqueous solution of sodium hydrogen carbonate and two 20-ml portions of a 10%w aqueous solution of sodium chloride. The washed organic phase was dried over anhydrous magnesium sulphate and the solvent was evaporated (2 kPa) from the dried liquid to leave a residue (2.3 g) containing the desired (100% (1R,cis), yield 63%). The nuclear magnetic resonance spectrum of this product showed the following absorptions (using a solution of this product in deuterochloroform and relative to a tetramethylsilane standard):

Workup

  1. stirringstirring
  2. waitwas continued for 16 hours
  3. customThe reaction mixture obtained
  4. customat 20° C.
  5. stirringstirring
  6. waitwas continued for 15 minutes
  7. filtrationthe suspended material was filtered off
  8. washthe filtrate was washed with two 20-ml portions of a saturated aqueous solution of sodium hydrogen carbonate and two 20-ml portions of a 10%w aqueous solution of sodium chloride
  9. dry with materialThe washed organic phase was dried over anhydrous magnesium sulphate
  10. customthe solvent was evaporated (2 kPa) from the dried liquid

Sources & evidence

ORD record
ord-0d5d585a1c1244378451204e33af0db9
Source dataset
uspto-grants-1980_09
Patent number
US04222964

Reaction notes

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