Toluene → 5-(2,3-Epoxypropyl)-5-hydroxy-10,11-dihydro-5H-dibenzo[a,d]cycloheptene

HRID 2413017Notes

Reaction equation

HRID 2413017 reaction equation
[CH2:1]([C:4]1([OH:19])[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=2[CH2:8][CH2:7][C:6]2[CH:15]=[CH:16][CH:17]=[CH:18][C:5]1=2)[CH:2]=[CH2:3].C([O:24]O)(C)(C)C.C1(C)C=CC=CC=1>CCCCCC.C/C(/O)=C/C(C)=O.C/C(/O)=C/C(C)=O.C/C(/O)=C/C(C)=O.[V]>[O:24]1[CH2:3][CH:2]1[CH2:1][C:4]1([OH:19])[C:5]2[CH:18]=[CH:17][CH:16]=[CH:15][C:6]=2[CH2:7][CH2:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]1=2

Participants

6

Reactant 3

HCID 1140TolueneHCID 6410tert-Butyl hydroperoxideHCID 905995-Allyl-10,11-dihydro-5H-dibenzo(a,d)cyclohepten-5-ol

Product 1

HCID 204314525-(2,3-Epoxypropyl)-5-hydroxy-10,11-dihydro-5H-dibenzo[a,d]cyclohepteneYield 50%

Reagents, catalysts & solvents 2

HCID 5377225Vanadium(III) acetylacetonateCatalystHCID 8058HexaneSolvent

Procedure

To a stirred, refluxing solution of 35.7 g (0.14 mol) of 5-allyl-5-hydroxy-10,11-dihydro-5H-dibenzo[a,d]cycloheptene 10 (R. D. Hoffsommer, et al, supra) in 500 ml of hexane was added 0.5 g of vanadium (III) acetylacetonate followed by the dropwise addition of 25.1 g (0.22 mol) of 70% tert-butylhydroperoxide. The resulting yellow mixture was refluxed for 4 hrs., then 100 ml of toluene was added. The reaction was allowed to cool to room temperature and stand for 12 hrs. Excess hydroperoxide was destroyed by the addition of 300 ml of aqueous sodium sulfite (Na2SO3) solution (10%). The organic phase was separated, dried over anhydrous MgSO4, filtered and evaporated. Recrystallization of the solid from CHCl3 -hexane gave 18.5 g (50% yield) of the epoxide 11, m.p. 116°-118° C.

Workup

  1. temperatureThe resulting yellow mixture was refluxed for 4 hrs
  2. customExcess hydroperoxide was destroyed by the addition of 300 ml of aqueous sodium sulfite (Na2SO3) solution (10%)
  3. customThe organic phase was separated
  4. dry with materialdried over anhydrous MgSO4
  5. filtrationfiltered
  6. customevaporated
  7. customRecrystallization of the solid from CHCl3 -hexane

Sources & evidence

ORD record
ord-92cf84b108054aae8b070cb79663080a
Source dataset
uspto-grants-1985_01
Patent number
US04495281

Reaction notes

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