Toluene → 3-(4'-Chloro-4-ethylbiphen-3-yl)bicyclo[3.2.1]oct-6-ene-2,4-dione

HRID 72255Notes

Reaction equation

HRID 72255 reaction equation
C([O-])(=O)C.C([O-])(=O)C.C([O-])(=O)C.[Cl:13][C:14]1[CH:28]=[CH:27][C:17]([C:18]2[CH:19]=[CH:20][C:21]([CH2:25][CH3:26])=[C:22]([Pb+3])[CH:23]=2)=[CH:16][CH:15]=1.[CH:29]12[CH2:36][CH:33]([CH:34]=[CH:35]1)[C:32](=[O:37])[CH2:31][C:30]2=[O:38].C1(C)C=CC=CC=1>C(Cl)(Cl)Cl.CN(C)C1C=CN=CC=1>[Cl:13][C:14]1[CH:28]=[CH:27][C:17]([C:18]2[CH:19]=[CH:20][C:21]([CH2:25][CH3:26])=[C:22]([CH:31]3[C:32](=[O:37])[CH:33]4[CH2:36][CH:29]([CH:35]=[CH:34]4)[C:30]3=[O:38])[CH:23]=2)=[CH:16][CH:15]=1

Participants

6

Reactant 3

HCID 1140TolueneHCID 58609530HCID 58609530, compoundHCID 178476534HCID 178476534, compound

Product 1

HCID 1317318283-(4'-Chloro-4-ethylbiphen-3-yl)bicyclo[3.2.1]oct-6-ene-2,4-dione

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6212ChloroformSolvent

Procedure

To a solution of 4′-chloro-4-ethylbiphen-3-yllead triacetate (0.478 g, 0.80 mmol) in chloroform (5 ml) is added bicyclo[3.2.1]oct-6-ene-2,4-dione (0.097 g, 0.72 mmol) (preparation described by R. Beaudegnies et al., WO2005/123667) and 4-dimethylaminopyridine (0.36 g, 2.86 mmol), and the reaction mixture is stirred at room temperature for 5 minutes. Next toluene (1 ml) is added, and the mixture is stirred at 80° C. for 2 hours (pre-heated oil bath). The reaction mixture is allowed to cool to room temperature, quenched with 2M hydrochloric acid and the inorganic precipitate removed by filtration. The organic phase is separated, and the aqueous phase is further washed with dichloromethane (×2), and again the phases are separated. All organics are combined then evaporated under reduced pressure to give a brown gum. This crude product is first purified by preparative reverse-phase HPLC, then also by flash column chromatography on silica gel (20% to 100% ethyl acetate/hexane eluant ratio) to afford 3-(4′-chloro-4-ethylbiphen-3-yl)bicyclo[3.2.1]oct-6-ene-2,4-dione.

Workup

  1. stirringthe mixture is stirred at 80° C. for 2 hours
  2. temperature(pre-heated oil bath)
  3. temperatureto cool to room temperature
  4. customquenched with 2M hydrochloric acid
  5. customthe inorganic precipitate removed by filtration
  6. customThe organic phase is separated
  7. washthe aqueous phase is further washed with dichloromethane (×2)
  8. customagain the phases are separated
  9. customAll organics are combined then evaporated under reduced pressure
  10. customto give a brown gum
  11. customThis crude product is first purified by preparative reverse-phase HPLC

Sources & evidence

ORD record
ord-c00c5f8842cf40a08262af178ea69ec7
Source dataset
uspto-grants-2014_09
Patent number
US08828908B2

Reaction notes

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