Hydrochloric Acid → 3,4-Dihydro-1'-[2-(benzofurazan-5-oxy)ethyl]-6-methanesulfonamidospiro[(2H)-1-benzopyran-2,4'-piperidine]-4-one hydrochloride

HRID 1591179Notes

Reaction equation

HRID 1591179 reaction equation
Br[CH2:2][CH2:3][O:4][C:5]1[CH:6]=[CH:7][C:8]2[C:9]([CH:13]=1)=[N:10][O:11][N:12]=2.[ClH:14].[CH3:15][S:16]([NH:19][C:20]1[CH:21]=[CH:22][C:23]2[O:33][C:27]3([CH2:32][CH2:31][NH:30][CH2:29][CH2:28]3)[CH2:26][C:25](=[O:34])[C:24]=2[CH:35]=1)(=[O:18])=[O:17].C(=O)(O)[O-].[Na+].[I-].[K+].Cl>C(#N)C.CCOC(C)=O>[ClH:14].[N:12]1[O:11][N:10]=[C:9]2[CH:13]=[C:5]([O:4][CH2:3][CH2:2][N:30]3[CH2:31][CH2:32][C:27]4([CH2:26][C:25](=[O:34])[C:24]5[CH:35]=[C:20]([NH:19][S:16]([CH3:15])(=[O:17])=[O:18])[CH:21]=[CH:22][C:23]=5[O:33]4)[CH2:28][CH2:29]3)[CH:6]=[CH:7][C:8]=12

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 4875Potassium IodideHCID 516892Sodium Bicarbonate2×HCID 19045253N-(4-Oxospiro[chroman-2,4'-piperidine]-6-yl)methanesulfonamide hydrochlorideHCID 190453515-(2-Bromoethoxy)benzofurazan

Product 1

HCID 190454533,4-Dihydro-1'-[2-(benzofurazan-5-oxy)ethyl]-6-methanesulfonamidospiro[(2H)-1-benzopyran-2,4'-piperidine]-4-one hydrochlorideYield 62.2%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

5-(2-Bromoethoxy)benzofurazan (87 mg, 0.36 mmol), 3,4-Dihydro-6-methanesulfonamidospiro[(2H)-1-benzopyran-2,4'-piperidine]-4-one hydrochloride (125 mg, 0.36 mmol), sodium bicarbonate (91 mg, 1.08 mmol) and potassium iodide (30 mg, 0.18 mmol) in acetonitrile (4 ml) were heated under reflux for 24 hr, cooled and aqueous sodium bicarbonate (saturated, 10 ml) was added. The mixture was extracted with dichloromethane (3×10 ml) and 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 (97:3:0.3), to give a yellow foam which was dissolved in EtOAc (2 ml). Ethanolic HCl (Ca. 1M, 2 ml) was added, the mixture was stirred for 2 h. and the solid was collected and dried in vacuo to give the hydrochloride as a white solid (114 mg, 62%), m.p.>250° C.

Workup

  1. temperatureunder reflux for 24 hr
  2. temperaturecooled
  3. extractionThe mixture was extracted with dichloromethane (3×10 ml)
  4. dry with materialthe combined organic fractions were dried (Na2SO4)
  5. customevaporated under reduced pressure
  6. customThe residue was purified by flash column chromatography on silica gel
  7. washeluting with CH2Cl2 /MeOH/NH3 (97:3:0.3)
  8. customto give a yellow foam which
  9. customthe solid was collected
  10. customdried in vacuo

Sources & evidence

ORD record
ord-b987268f2be34ecab99f56c899b39dee
Source dataset
uspto-grants-1993_04
Patent number
US05206240

Reaction notes

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