Hydroquinone → (4aS,8aS)-2-Benzoyl-4a-(3-methoxyphenyl)octahydroisoquinolin-6(2H)-one

HRID 1155367Notes

Reaction equation

HRID 1155367 reaction equation
C([Li])CCC.Br[C:7]1[CH:8]=[C:9]([O:13][CH3:14])[CH:10]=[CH:11][CH:12]=1.C1(C=CC(O)=CC=1)O.[C:23]([N:31]1[CH2:40][CH2:39][C:38]2[CH:33]([CH2:34][CH2:35][C:36](=[O:41])[CH:37]=2)[CH2:32]1)(=[O:30])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.S([O-])([O-])(=O)=O.[NH4+].[NH4+]>[Cu]I.O.O1CCCC1>[C:23]([N:31]1[CH2:40][CH2:39][C@@:38]2([C:7]3[CH:12]=[CH:11][CH:10]=[C:9]([O:13][CH3:14])[CH:8]=3)[C@H:33]([CH2:34][CH2:35][C:36](=[O:41])[CH2:37]2)[CH2:32]1)(=[O:30])[C:24]1[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1

Participants

9

Reactant 5

HCID 785HydroquinoneHCID 169713-BromoanisoleHCID 3473462-benzoyl-1,3,4,7,8,8a-hexahydroisoquinolin-6-oneHCID 6097028Ammonium SulfateHCID 178418339Butyllithium

Product 1

HCID 71372021(4aS,8aS)-2-Benzoyl-4a-(3-methoxyphenyl)octahydroisoquinolin-6(2H)-one

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

278 ml. of 2.2 N butyl lithium solution (612 mmol) are added to a mixture of 600 ml of absolute tetrahydrofuran, 112.2 g (600 mmol) of 3-bromoanisole and 661 mg (6 mmol) of hydroquinone at -65° under nitrogen. The resulting mixture is kept at -50° for 30 minutes, treated with 57.13 g (0.3 mol) of copper (I) iodide, stirred for 1 hour at -43°, and treated with 51.06 g (0.2 mol) of 1,3,4,7,8,8a-hexahydro-2-benzoyl-6(2H)-isoquinolinone. The mixture is allowed to warm to 0° over 2 hours and kept at 0° for 16 hours. 1.2 liters of water and 79.28 g (0.6 mol) of ammonium sulphate are added to the mixture which is then extracted with toluene. The organic extracts are evaporated to yield an oil which is chromatographed on silicagel using ethyl acetate as eluant. The product, 2-benzoyl-octahydro-4a-(3-methoxyphenyl)-cis-6(2H)-iso-quinolinone is obtained as colourless crystals from methanol; M.Pt. 78°.

Workup

  1. temperatureto warm to 0° over 2 hours
  2. waitkept at 0° for 16 hours
  3. extractionis then extracted with toluene
  4. customThe organic extracts are evaporated
  5. customto yield an oil which
  6. customis chromatographed on silicagel

Sources & evidence

ORD record
ord-52fdd352098440c583335d92ed7649ec
Source dataset
uspto-grants-1981_11
Patent number
US04301290

Reaction notes

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