Hydrochloric Acid → 1H-Imidazole-1-sulfonyl azide hydrochloride

HRID 1896224Notes

Reaction equation

HRID 1896224 reaction equation
[N-:1]=[N+:2]=[N-:3].[Na+].[S:5](Cl)([Cl:8])(=[O:7])=[O:6].[NH:10]1[CH:14]=[CH:13][N:12]=[CH:11]1.Cl>C(OCC)(=O)C.C(#N)C>[ClH:8].[N:10]1([S:5]([N:1]=[N+:2]=[N-:3])(=[O:7])=[O:6])[CH:14]=[CH:13][N:12]=[CH:11]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 795ImidazoleHCID 24648Sulfuryl chlorideHCID 33557Sodium Azide

Product 1

HCID 235839821H-Imidazole-1-sulfonyl azide hydrochlorideYield 49.9%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A modification of a published procedure was used (19). A suspension of 6.53 g NaN3 (25, 100 mmol, Aldrich, >99.5%) and 100 mL acetonitrile (Aldrich, 99.8% anhydrous) in a 500-mL round-bottom flask was cooled in an ice water bath under a flow of nitrogen. Then was added 8.15 mL sulfuryl chloride (100 mmol, TCI American, >98.0%) in 20 mL) anhydrous acetonitrile drop-wise to the ice-cooled suspension. The mixture was stirred overnight at room temperature, after which we cooled the white suspension to −0° C. with ice water and added 13.03 g imidazole (191 mmol, TCI America, >98.0%). The resulting white slurry was warmed to room temperature, then stirred for 3 h. It was diluted with ethyl acetate (200 mL) and separated and discarded the aqueous layer. The organic layer was washed twice with deionized water (2×100 mL), then twice with saturated aqueous NaHCO3 (2×100 mL). It was dried over anhydrous MgSO4 overnight and filtered. Ethanolic HCl solution (196 mmol) was added drop-wise to the filtrate while stirring at ice-water temperature. After the addition of −3 mL, a large amount of white solid appeared. The mixture was kept in an ice bath for 15 min, then at room temperature for 30 min, after which it was filtered. The filter cake was washed with ethyl acetate (3×100 mL) to obtain 126 as a colorless solid (8.65 g, 49.9%), m.p. 99-101° C. IR (KBr) 2173, 1383 and 1160 cm−1. 1H NMR (500 MHz, D2O) δ 7.61 (dd), 8.02 (dd), 9.39 (dd); 13C NMR (125. MHz, D2O) δ=120.0, 123.5, 137.6. Element Analysis Calculated C, 17.19; H, 1.92; N, 33.41. Found: C, 17.38; H, 1.98; N, 32.97.

Workup

  1. temperaturewas cooled in an ice water bath under a flow of nitrogen
  2. temperaturecooled suspension
  3. temperatureThe resulting white slurry was warmed to room temperature
  4. stirringstirred for 3 h
  5. customseparated
  6. washThe organic layer was washed twice with deionized water (2×100 mL)
  7. dry with materialIt was dried over anhydrous MgSO4 overnight
  8. filtrationfiltered
  9. additionAfter the addition of −3 mL
  10. waitThe mixture was kept in an ice bath for 15 min
  11. waitat room temperature for 30 min
  12. filtrationafter which it was filtered
  13. washThe filter cake was washed with ethyl acetate (3×100 mL)

Sources & evidence

ORD record
ord-294513a9619d48ecafa045a3453f52fb
Source dataset
uspto-grants-2013_08
Patent number
US08518957B2

Reaction notes

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