Sulfuric Acid → HCID 15670606, compound

HRID 233773Notes

Reaction equation

HRID 233773 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[C:3]=1[S:12]([CH:15]1[S:19][C:18](=[O:20])[NH:17][C:16]1=[O:21])(=[O:14])=[O:13].S1CC(=O)NC1=O.C([Li])CCC.[Br:34]C1C=CC=C2C=1C=CC=C2S(Cl)(=O)=O.S(=O)(=O)(O)O>O1CCCC1>[Br:34][C:8]1[CH:7]=[CH:6][CH:5]=[C:4]2[C:9]=1[CH:10]=[CH:11][CH:2]=[C:3]2[S:12]([CH:15]1[S:19][C:18](=[O:20])[NH:17][C:16]1=[O:21])(=[O:14])=[O:13]

Participants

7

Reactant 5

HCID 1118Sulfuric AcidHCID 5437ThiazolidinedioneHCID 132502755-Bromonaphthalene-1-sulfonyl chlorideHCID 86750193HCID 86750193, compoundHCID 178418339Butyllithium

Product 1

HCID 15670606HCID 15670606, compoundYield 42%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

5-[(Bromo-1-naphthalenyl)sulfonyl]-2,4-thiazolidinedione. To a stirred solution of 2,4-thiazolidinedione (5.5 g, 47 mmol) in tetrahydrofuran (THF) (275 mL) at -78° C. under nitrogen was added n-butyllithium (62 mL, 99 mmol) portionwise over 15 minutes. The mixture was maintained at -78° C. for 15 minutes and then warmed to 0° C. for 30 minutes to complete the dianion formation. Upon recooling to -78° C., 5-bromo-1-naphthalene-sulfonyl chloride (16 g, 52 mmol) was added as a solid, all at once. After 30 minutes the solution was allowed to warm to 25° C. After 1.5 hours the reaction mixture was treated with 5% aqueous sulfuric acid. The aqueous phase was washed with chloroform (3×), and the combined organic extracts were concentrated to an oil which was taken up in 5% aqueous sodium bicarbonate and extracted with chloroform (3×). The combined organic extracts of the acidified aqueous phase were dried (magnesium sulfate) and then concentrated to give an oil, which was purified by chromatography (acid-washed silica gel, 10:1 chloroform/acetonitrile) to give 5-[(5-Bromo-1-naphthalenyl)sulfonyl]-2,4-thiazolidinedione (7.6 g, 42% yield): mp 189°-190° C. (acetonitrile/chloroform): 1H NMR (DMSO-d6, 200 MHz) δ6.60 (s, 1H, CH, exchanges with D2O), 7,7-8.7 (m, 6H, ArH).

Workup

  1. temperaturewarmed to 0° C. for 30 minutes
  2. customUpon recooling to -78° C.
  3. temperatureto warm to 25° C
  4. washThe aqueous phase was washed with chloroform (3×)
  5. concentrationthe combined organic extracts were concentrated to an oil which
  6. extractionextracted with chloroform (3×)
  7. dry with materialThe combined organic extracts of the acidified aqueous phase were dried (magnesium sulfate)
  8. concentrationconcentrated
  9. customto give an oil, which
  10. customwas purified by chromatography (acid-washed silica gel, 10:1 chloroform/acetonitrile)

Sources & evidence

ORD record
ord-e36faa03b744491b8070c15b37a38b20
Source dataset
uspto-grants-1997_01
Patent number
US05594015

Reaction notes

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