Hydrochloric Acid → Ethyl[(3,4-dihydro-1'-[2-(benzofurazan-5-yl)ethyl]-4-oxo-spiro[(2H)-1-benzopyran-2,4'-piperidine]-6-yl)amino]sulfonyl acetate hydrochloride

HRID 1781424Notes

Reaction equation

HRID 1781424 reaction equation
[Cl:1][S:2](CC(OCC)=O)(=[O:4])=[O:3].[NH2:11][C:12]1[CH:13]=[CH:14][C:15]2[O:36][C:19]3([CH2:24][CH2:23][N:22]([CH2:25][CH2:26][C:27]4[CH:28]=[CH:29][C:30]5[C:31]([CH:35]=4)=[N:32][O:33][N:34]=5)[CH2:21][CH2:20]3)[CH2:18][C:17](=[O:37])[C:16]=2[CH:38]=1.N1[CH:44]=[CH:43]C=CC=1.[C:45](=[O:48])([O-])[OH:46].[Na+].Cl.[CH3:51]N(C=O)C>C(OCC)(=O)C>[ClH:1].[C:45]([O:46][S:2]([N:11]([CH2:43][CH3:44])[C:12]1[CH:13]=[CH:14][C:15]2[O:36][C:19]3([CH2:20][CH2:21][N:22]([CH2:25][CH2:26][C:27]4[CH:28]=[CH:29][C:30]5[C:31]([CH:35]=4)=[N:32][O:33][N:34]=5)[CH2:23][CH2:24]3)[CH2:18][C:17](=[O:37])[C:16]=2[CH:38]=1)(=[O:4])=[O:3])(=[O:48])[CH3:51]

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 1049PyridineHCID 6228Dimethylformamide2×HCID 516892Sodium BicarbonateHCID 12225100Ethyl (chlorosulfonyl)acetate2×HCID 190452936-Amino-3,4-dihydro-1'-[2-(benzofurazan-5-yl)ethyl]-spiro[(2H)-1-benzopyran-2,4'-piperidine]-4-one

Product 1

HCID 19045297Ethyl[(3,4-dihydro-1'-[2-(benzofurazan-5-yl)ethyl]-4-oxo-spiro[(2H)-1-benzopyran-2,4'-piperidine]-6-yl)amino]sulfonyl acetate hydrochlorideYield 61%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

Ethyl chlorosulfonylacetate (140 mg, 0.75 mmol) in DMF (1 ml) was added dropwise to a stirred solution of 6-amino-3,4-dihydro-1'-[2-(benzofurazan-5-yl)-ethyl]-spiro[(2H)-1-benzopyran-2,4'-piperidine]-4-one (189 mg, 0.5 mmol) and pyridine (40 mg, 3 mmol) in DMF (5 ml). The mixture was stirred for 4 hours, then additional ethyl chlorosulfonylacetate (46 mg, 0.25 mmol) was added. The mixture was stirred for 1 hour, poured into aqueous sodium hydrogen carbonate (saturated, 25 ml) and extracted with dichloromethane (3×25 ml). The combined organic fractions were dried (Na2SO4) and evaporated under reduced pressure. The residue was purified by flash column chromatography on silica gel, eluting with CH2Cl2 /MeOH/NH3 (Aq.). (97:3:0.3) to give a yellow foam which was dissolved in ethyl acetate (2 ml) and treated with ethanolic HCl (6N, 0.5 ml). The mixture was stirred for 1 hour, cooled and the solid was collected and dried in vacuo to give the hydrochloride as a white solid (171 mg, 61%), m.p. 250°-251° C.

Workup

  1. stirringThe mixture was stirred for 1 hour
  2. extractionextracted with dichloromethane (3×25 ml)
  3. dry with materialThe combined organic fractions were dried (Na2SO4)
  4. customevaporated under reduced pressure
  5. customThe residue was purified by flash column chromatography on silica gel
  6. washeluting with CH2Cl2 /MeOH/NH3 (Aq.)
  7. custom(97:3:0.3) to give a yellow foam which
  8. stirringThe mixture was stirred for 1 hour
  9. temperaturecooled
  10. customthe solid was collected
  11. customdried in vacuo

Sources & evidence

ORD record
ord-ea8def37ace8456b89df8f614a449e68
Source dataset
uspto-grants-1997_05
Patent number
US05633247

Reaction notes

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