4-Toluenesulfonyl chloride → trans-(-)-Octahydro-7-[[[(4-methylphenyl)sulfonyl]oxy]methylene]-1-(n-propyl)-6(2H)-quinolinone

HRID 34981Notes

Reaction equation

HRID 34981 reaction equation
C[C:2](C)([O-:4])C.[K+].[CH2:7]([N:10]1[C@H:19]2[C@@H:14]([CH2:15][C:16](=[O:20])[CH2:17][CH2:18]2)[CH2:13][CH2:12][CH2:11]1)[CH2:8][CH3:9].C(OCC)=O.[C:26]1([CH3:36])[CH:31]=[CH:30][C:29]([S:32](Cl)(=[O:34])=[O:33])=[CH:28][CH:27]=1>O1CCCC1.C(O)(=O)C>[CH3:36][C:26]1[CH:31]=[CH:30][C:29]([S:32]([O:4][CH:2]=[C:17]2[CH2:18][C@@H:19]3[C@H:14]([CH2:13][CH2:12][CH2:11][N:10]3[CH2:7][CH2:8][CH3:9])[CH2:15][C:16]2=[O:20])(=[O:34])=[O:33])=[CH:28][CH:27]=1

Participants

7

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 8025Ethyl formateHCID 13457872(8aR-trans)-octahydro-1-propyl-6(2H)-quinolinoneHCID 23665647Potassium tert-butoxide

Product 1

HCID 86742333trans-(-)-Octahydro-7-[[[(4-methylphenyl)sulfonyl]oxy]methylene]-1-(n-propyl)-6(2H)-quinolinone

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
-15 °C

Procedure

A 1 l. 3-neck round bottom flask was purged with nitrogen and charged with 35.0 g (0.312 mol) of potassium t-butoxide. Next, 348 ml of dry tetrahydrofuran was added to the flask and the resulting mixture was cooled to about -15° C. with stirring. To this mixture was added a solution of 30.3 g (0.155 mol) of (8aR-trans)-(-)-octahydro-1-(n-propyl)-6-(2H)-quinolinone in 30 ml of tetrahydrofuran over a period of about 9 minutes while maintaining the temperature of the reaction mixture between about -15° C. and about -17° C. The stirred reaction mixture was allowed to warm to room temperature and the mixture was stirred for 1 hour. The reaction mixture was cooled to about -25° C. and a solution of 23.1 g (25.2 ml, 0.31 mol) of ethyl formate in 45 ml of tetrahydrofuran was added dropwise to the reaction mixture over a period of about 21 minutes. The resulting mixture was stirred for about 30 minutes at about -25° C. and was allowed to warm to about 5° C. The mixture was cooled to about -15° C. and held at that temperature for about 60 hours. The mixture was warmed to about 0° C. and charged with 8.9 ml of glacial acetic acid dropwise. The stirred reaction mixture was cooled to about -37° C. To the mixture was added a solution of 32.6 g (0.171 mol) of p-toluenesulfonyl chloride dissolved in 45 ml of tetrahydrofuran over a period of about 5 minutes. The reaction mixture was warmed to about 0° C. over a period of about 65 minutes and the mixture was held at this temperature for 17.5 hours. The title compound thus prepared was held in situ for further processing.

Workup

  1. custom3-neck round bottom flask was purged with nitrogen
  2. temperaturewhile maintaining the temperature of the reaction mixture between about -15° C. and about -17° C
  3. customThe stirred reaction mixture
  4. temperatureto warm to room temperature
  5. stirringthe mixture was stirred for 1 hour
  6. temperatureThe reaction mixture was cooled to about -25° C.
  7. stirringThe resulting mixture was stirred for about 30 minutes at about -25° C.
  8. temperatureto warm to about 5° C
  9. temperatureThe mixture was cooled to about -15° C.
  10. temperatureThe mixture was warmed to about 0° C.
  11. customThe stirred reaction mixture
  12. temperaturewas cooled to about -37° C
  13. temperatureThe reaction mixture was warmed to about 0° C. over a period of about 65 minutes
  14. waitthe mixture was held at this temperature for 17.5 hours

Sources & evidence

ORD record
ord-d54822879ad64c44a320d371522417f1
Source dataset
uspto-grants-1988_08
Patent number
US04764609

Reaction notes

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