Hydrochloric Acid → HCID 14477105, compound

HRID 893388Notes

Reaction equation

HRID 893388 reaction equation
Cl[O-].[Na+].[OH-].[Na+].C([CH:9]1[CH:14]([C:15](=O)[NH2:16])[CH:13]2[CH2:18][CH:10]1CC2)(O)=O.Cl.[C:20]1([S:26](Cl)(=[O:28])=[O:27])[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.[C:30]([O:33]CC)(=[O:32])[CH3:31]>>[C:30]([CH:31]1[CH:15]([NH:16][S:26]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)(=[O:28])=[O:27])[CH:14]2[CH2:9][CH:10]1[CH2:18][CH2:13]2)([OH:33])=[O:32]

Participants

7

Reactant 6

HCID 313Hydrochloric AcidHCID 7369Benzenesulfonyl chloride2×HCID 8857Ethyl AcetateHCID 14798Sodium Hydroxide4×HCID 19892517HCID 19892517, compoundHCID 23665760Sodium Hypochlorite

Product 1

HCID 14477105HCID 14477105, compoundYield 81.8%

Procedure

To a solution of 141.59 g (275 mmol) of sodium hypochlorite (14.7% aqueous solution) and 206 ml (275 mmol×1.5) of 2N NaOH at 25° C. is added a solution of 50.39 g (275 mmol) of 2-carboxy-3-carbamoylnorbornane (2a'), prepared in above 1, in 138 ml (275 mmol) of 2N NaOH. While the mixture is stirred for 1 hour, the temperature rises upto approximately 30° C. Upon continuous stirring for about 30 minutes on a bath of 125° C., the inner temperature rises upto 100° C. After refluxing for 15 minutes, the reaction mixture is promptly cooled to room temperature and then ice-cooled. The pH of the ice-cooled mixture is adjusted to about 3 to 4 with conc. HCl and washed with ethyl acetate. The aqueous layer is separated, washed with dichloromethane, and adjusted to pH 11 with 5N NaOH. To the resulting mixture is added 52.6 ml (275 mmol×1.5) of benzenesulfonyl chloride at 25° C. and the mixture stirred for 30 minutes with monitoring the pH of the reaction, mixture. When the pH becomes to about 6-7, 55 ml (275 mmol) of 5N NaOH and 17.5 ml (275 mM×0.5) of benzenesulfonyl chloride are added thereto. To the mixture is then added 55 ml (275 mM) of 5N NaOH and stirring is continued for another 40 minutes. Ethyl acetate is added to the reaction mixture and the aqueous layer is separated. The aqueous layer is acidified with conc. HCl and extracted with ethyl acetate. The ethyl acetate layer is dried over MgSO4 and concentrated to obtain a residue. Recrystallization from a mixture of toluene and ethyl acetate gives 66.4 g of 2-carboxy-3-phenylsulfonylaminonorbornane (Ia'). Yield=81.8%; m.p.=157°-159° C.

Workup

  1. customrises upto approximately 30° C
  2. stirringUpon continuous stirring for about 30 minutes on a bath of 125° C.
  3. customrises upto 100° C
  4. temperatureAfter refluxing for 15 minutes
  5. temperatureice-cooled
  6. washwashed with ethyl acetate
  7. customThe aqueous layer is separated
  8. washwashed with dichloromethane
  9. stirringthe mixture stirred for 30 minutes
  10. customthe pH of the reaction, mixture
  11. additionare added
  12. stirringstirring
  13. waitis continued for another 40 minutes
  14. customthe aqueous layer is separated
  15. extractionextracted with ethyl acetate
  16. dry with materialThe ethyl acetate layer is dried over MgSO4
  17. concentrationconcentrated
  18. customto obtain a residue
  19. customRecrystallization
  20. additionfrom a mixture of toluene and ethyl acetate

Sources & evidence

ORD record
ord-d9a2a9364adc42bba62c346c007aef1f
Source dataset
uspto-grants-1992_06
Patent number
US05124462

Reaction notes

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