Carbon Dioxide → HCID 19759880, compound

HRID 1586867Notes

Reaction equation

HRID 1586867 reaction equation
[S:1]1(=[O:10])(=[O:9])[C:5]2[S:6][CH:7]=[CH:8][C:4]=2[CH2:3][CH2:2]1.C([Li])CCC.[C:16](=[O:18])=[O:17]>C1COCC1.CCCCCC.CCOCC>[S:1]1(=[O:10])(=[O:9])[C:5]2[S:6][CH:7]=[CH:8][C:4]=2[CH2:3][CH:2]1[C:16]([OH:18])=[O:17]

Participants

7

Reactant 3

HCID 280Carbon DioxideHCID 19759867HCID 19759867, compoundHCID 178418339Butyllithium

Product 1

HCID 19759880HCID 19759880, compoundYield 47%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

2,3-Dihydrothieno[2,3-b]thiophene-1,1-dioxide (35.5 g, 0.204 mol) in THF (300 mL) was cooled to -78° C. under a nitrogen atmosphere. A solution of n-butyllithium in hexane (82.7 mL, 2.47M) was added dropwise over a period of 1 hour. The dark red solution was stirred for an additional 15 minutes and poured over dry ice (2 L) in ether (2 L). The reaction was allowed to warm to room temperature and the product partitioned between aqueous sodium hydroxide and ether. The aqueous phase was extracted twice with ethyl acetate, then rendered acidic (pH 1) with concentrated HCl. The resulting yellow suspension was extracted into ethyl acetate. The ethyl acetate solution was washed with saturated brine and dried over magnesium sulfate, filtered, and the solvent removed in vacuo to provide an 8:2 mixture of carboxylic acids. The solid was triturated with 5% acetonitrile in ether and collected by filtration. This was repeated a total of four times to remove most of the undesired minor product. The filtrates from the washings were combined to give approximately 1:1 mixture of carboxylic acids (17.6 g, 39%), which could be separated by column chromatography on silica gel with 10% acetic acid in chloroform. The filtered product was a light tan powder which was dried in a vacuum oven at 20° C. under house vacuum overnight to provide the title compound (21.3 g, 47%) in >95% purity.

Workup

  1. customthe product partitioned between aqueous sodium hydroxide and ether
  2. extractionThe aqueous phase was extracted twice with ethyl acetate
  3. extractionThe resulting yellow suspension was extracted into ethyl acetate
  4. washThe ethyl acetate solution was washed with saturated brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. customthe solvent removed in vacuo
  8. customto provide
  9. customThe solid was triturated with 5% acetonitrile in ether
  10. filtrationcollected by filtration
  11. customto remove most of the undesired minor product
  12. customto give approximately
  13. customcould be separated by column chromatography on silica gel with 10% acetic acid in chloroform
  14. customwas dried in a vacuum oven at 20° C. under house vacuum overnight

Sources & evidence

ORD record
ord-4d9eff50ec0e4606b027d7cd922b04d4
Source dataset
uspto-grants-1993_06
Patent number
US05216020

Reaction notes

Loading…