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

HRID 127018Notes

Reaction equation

HRID 127018 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 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. waitwas continued for 16 hours
  5. customThe reaction mixture obtained
  6. customat 20° C.
  7. stirringstirring
  8. waitwas continued for 15 minutes
  9. filtrationthe suspended material was filtered off
  10. 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
  11. dry with materialThe washed organic phase was dried over anhydrous magnesium sulphate
  12. customthe solvent was evaporated (2 kPa) from the dried liquid

Sources & evidence

ORD record
ord-9e1b26dacbb94a8d952834409461c538
Source dataset
uspto-grants-1981_03
Patent number
US04254280

Reaction notes

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