Sodium Iodide → HCID 67692893, compound

HRID 1033083Notes

Reaction equation

HRID 1033083 reaction equation
C1OCCOCCOCCOCCOCCOC1.[Na+].[I-].[CH2:21]([NH:23][C@H:24]1[CH2:29][C@H:28]([CH2:30][O:31][CH2:32][CH2:33][O:34]C)[S:27](=[O:37])(=[O:36])[C:26]2[S:38][C:39]([S:41]([NH2:44])(=[O:43])=[O:42])=[CH:40][C:25]1=2)[CH3:22].B(Br)(Br)Br.C(Cl)[Cl:50]>CCOCC>[ClH:50].[CH2:21]([NH:23][CH:24]1[CH2:29][CH:28]([CH2:30][O:31][CH2:32][CH2:33][OH:34])[S:27](=[O:36])(=[O:37])[C:26]2[S:38][C:39]([S:41]([NH2:44])(=[O:43])=[O:42])=[CH:40][C:25]1=2)[CH3:22]

Participants

7

Reactant 5

HCID 5238Sodium IodideHCID 6344Dichloromethane2×HCID 25134Boron tribromideHCID 2855718-Crown-6HCID 86747814HCID 86747814, compound

Product 1

HCID 67692893HCID 67692893, compoundYield 13%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Under N2, 18-crown 6 (7.92 g, 0.03 mol) in CH2Cl2 (50 ml) and NaI (5 g, 0.033 mol) was stirred at room temperature. After 5 minutes, the reaction was cooled to 0°-4° C. and an ether solution of trans-5,6-dihydro-4-ethylamino-6-(2-methoxyethoxy) methyl-4H-thieno[2,3-b]thiopyran-2-sulfonamide-7,7-dioxide (2.1g, 0.005 mol) was added. After addition, the reaction was stirred at room temperature for 0.5 hours and then cooled to -78° C. and BBr3 in CH2Cl2 (1M, 25 ml, 0.025 mol) was added. After the addition, the reaction was allowed to warm to 0° C. over 3 hours. The mixture was then concentrated to dryness and the residue was treated with 6N HCl (40 ml). After heating for 5 minutes in a steam bath, the reaction was cooled and neutralized to pH 8.5 with NaHCO3. The resulting mixture was extracted with EtOAc(3×) and the organic extracts were dried, filtered and concentrated to dryness. The residue was chromatographed on a Still silica gel column and the product eluted with 25-50% methanol-chloroform with 2.5 to 5.0% aqueous NH3 to yield crude product. The material was crystallized as the HCl salt from EtOH to yield 280 mg (13%) of the title compound; m.p. 157°-9° C.

Workup

  1. temperaturethe reaction was cooled to 0°-4° C.
  2. additionAfter addition
  3. temperaturecooled to -78° C.
  4. additionAfter the addition
  5. temperatureto warm to 0° C. over 3 hours
  6. concentrationThe mixture was then concentrated to dryness
  7. additionthe residue was treated with 6N HCl (40 ml)
  8. temperatureAfter heating for 5 minutes in a steam bath
  9. temperaturethe reaction was cooled
  10. extractionThe resulting mixture was extracted with EtOAc(3×)
  11. customthe organic extracts were dried
  12. filtrationfiltered
  13. concentrationconcentrated to dryness
  14. customThe residue was chromatographed on a Still silica gel column
  15. washthe product eluted with 25-50% methanol-chloroform with 2.5 to 5.0% aqueous NH3
  16. customto yield crude product
  17. customThe material was crystallized as the HCl salt from EtOH

Sources & evidence

ORD record
ord-a1708354f6504d7b895682f3c2c106a8
Source dataset
uspto-grants-1994_05
Patent number
US05308863

Reaction notes

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