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

HRID 34982Notes

Reaction equation

HRID 34982 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 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-25 °C

Procedure

A 22 l. round bottom flask was charged with 568.9 g (5.07 mol) of potassium t-butoxide under a nitrogen atmosphere. To the flask was added 4.1 l of dry tetrahydrofuran and the resulting slurry was cooled to approximately -25° C. To the slurry was added 500.0 g (2.56 mol) of (8aR-trans)-(-)-octahydro-1-(n-propyl)-6(2H)-quinolinone over a period of 15 minutes. The addition funnel was rinsed twice with 30 ml portions of dry tetrahydrofuran and the mixture was allowed to warm to about 12° C. over a period of about 90 minutes. The mixture was warmed to about 25° C. and held at that temperature for about one hour. The mixture was cooled to about -26° C. and 386.8 g (422 ml, 5.22 mol) of ethyl formate was added to the mixture dropwise over a period of about 30 minutes. The mixture was held at about 0° C. overnight, cooled to about -8° C. and 150.0 g of glacial acetic acid was added to the stirred mixture. The pH of the mixture was about 11 following addition of the acid. The mixture was cooled to about -40° C. and a solution of 534.3 g (2.8 mol) of p-toluenesulfonyl chloride in 1610 ml of dry tetrahydrofuran was added rapidly while maintaining the temperature below about -35° C. The mixture was warmed to about 0° C. and held at this temperature for about one hour. The tetrahydrofuran was evaporated from the mixture under vacuum and 2.46 l. of dry DMF was added. The resulting solution containing trans-(-)-octahydro-7-[[[(4-methylphenyl)sulfonyl]oxy]methylene]-1-(n-propyl)-6(2H)-quinolinone was held for further processing.

Workup

  1. washThe addition funnel was rinsed twice with 30 ml portions of dry tetrahydrofuran
  2. temperatureto warm to about 12° C. over a period of about 90 minutes
  3. temperatureThe mixture was warmed to about 25° C.
  4. temperatureThe mixture was cooled to about -26° C.
  5. waitThe mixture was held at about 0° C. overnight
  6. temperaturecooled to about -8° C.
  7. addition11 following addition of the acid
  8. temperatureThe mixture was cooled to about -40° C.
  9. temperaturewhile maintaining the temperature below about -35° C
  10. temperatureThe mixture was warmed to about 0° C.
  11. waitheld at this temperature for about one hour
  12. customThe tetrahydrofuran was evaporated from the mixture under vacuum and 2.46 l
  13. additionof dry DMF was added
  14. additionThe resulting solution containing trans-(-)-octahydro-7-[[[(4-methylphenyl)sulfonyl]oxy]methylene]-1-(n-propyl)-6(2H)-quinolinone

Sources & evidence

ORD record
ord-40db391aba3f451ea73de51f4a226fbf
Source dataset
uspto-grants-1988_08
Patent number
US04764609

Reaction notes

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