Dimethyl Sulfide → HCID 86752386, compound

HRID 1417778Notes

Reaction equation

HRID 1417778 reaction equation
[C:1]([C:4]1[CH:5]=[CH:6][C:7]([O:14][CH2:15][CH2:16][CH2:17]C=C)=[C:8]([CH:13]=1)[C:9]([O:11][CH3:12])=[O:10])(=[O:3])[CH3:2].O=[O+][O-].CSC.[Cr](O[Cr]([O-])(=O)=O)([O-])(=O)=[O:27].[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1.CN(C)[CH:49]=[O:50]>C(Cl)Cl.O>[C:1]([C:4]1[CH:5]=[CH:6][C:7]([O:14][CH2:15][CH2:16][CH2:17][C:49]([OH:50])=[O:27])=[C:8]([CH:13]=1)[C:9]([O:11][CH3:12])=[O:10])(=[O:3])[CH3:2]

Participants

8

Reactant 5

HCID 1068Dimethyl SulfideHCID 6228DimethylformamideHCID 24823OzoneHCID 2724130Cornforth reagentHCID 86752381HCID 86752381, compound

Product 1

HCID 86752386HCID 86752386, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

Procedure

A sample of 0.203 g (0.775 mmol) of 5-acetyl-2-(4-pentenyloxy)benzoic acid, methyl ester is dissolved in 5 mL of methylene dichloride, under an argon atmosphere, and cooled to -78° C. in a dry ice acetone bath, with stirring. Next, ozone gas is passed through this solution for 10 min, until it turns a light bluish color. Then 0.5 mL of dimethyl sulfide is added to quench the reaction and it is allowed to warm to room temperature for 2 hours. The mixture is then evaporated under high vacuum, leaving the crude aldehyde product as an oil which is used "as is" for the second step. It is dissolved in 5 mL of N,N-dimethylformamide, and 1.02 g (2.71 mmol) of pyridinium dichromate is added. This reaction mixture is sealed and allowed to stand for 20 hours. It is next poured into 50 mL of water, extracted with ether, and the organic phase is washed with water again, dried with magnesium sulfate, filtered, and evaporated, which gives oily crystals. These are recrystallized from a mixture of ethyl acetate and hexane, producing 0.109 g (50%) of 5-acetyl-2-(3-carboxypropoxy)benzoic acid, methyl ester as white crystals: m.p. 111°-113° C.; IR (KBr) 1725, 1645 cm-1 ; 1HNMR (CDCl3) is consistent with the desired product; MS (FAB) m/e 281 (M+ +H). Analysis calculated for C14Hl6O6 : C, 60.00; H, 5.75; O, 34.25. Found: C, 59.96; H, 5.75; O, 34.27.

Workup

  1. customto quench
  2. customthe reaction and it
  3. temperatureto warm to room temperature for 2 hours
  4. customThe mixture is then evaporated under high vacuum
  5. customleaving the crude aldehyde product as an oil which
  6. customThis reaction mixture is sealed
  7. extractionextracted with ether
  8. washthe organic phase is washed with water again
  9. dry with materialdried with magnesium sulfate
  10. filtrationfiltered
  11. customevaporated
  12. customwhich gives oily crystals
  13. customThese are recrystallized from a mixture of ethyl acetate and hexane

Sources & evidence

ORD record
ord-bc70c61235c44911b8e7a617b7528f00
Source dataset
uspto-grants-1999_03
Patent number
US05877296

Reaction notes

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