Chloroform → 1-methoxy-6,7,8,9-tetrahydro-5H-benzo[7]annulen-6-one

HRID 523496Notes

Reaction equation

HRID 523496 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[CH:11][CH:10]=[C:9]2[C:4]=1[CH2:5][CH2:6][CH2:7][C:8]2=[CH2:13].O.O.O.[N+]([O-])([O-])=[O:18].[Tl+3].[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.C(Cl)(Cl)Cl>CO>[CH3:1][O:2][C:3]1[C:4]2[CH2:5][CH2:6][CH2:7][C:13](=[O:18])[CH2:8][C:9]=2[CH:10]=[CH:11][CH:12]=1

Participants

5

Reactant 3

HCID 6212ChloroformHCID 11270721Nitric acid,thallium(3+) salt, trihydrate (9CI)HCID 116080075-Methoxy-1-methylene-1,2,3,4-tetrahydronaphthalene

Product 1

HCID 127282361-methoxy-6,7,8,9-tetrahydro-5H-benzo[7]annulen-6-one

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

5-Methoxy-1-methylene-1,2,3,4-tetrahydro-naphthalene (23.8 g, 0.137 mol) in 150 mL MeOH added in one portion to freshly prepared solution of thallium(III)nitrate trihydrate (1.0 eq) in 300 mL MeOH. Stirred one minute and 400 mL chloroform added. The solution was filtered and the organics partitioned between dichloromethane and water. The organics were dried (MgSO4) and concentrated. Purification by chromatography (ISCO, 330 g silica cartridge; stepwise elution hexane (5 min) then 7 minute gradient to 100% dicloromethane (20 min) affords the title compound as the most polar of the products as a pale yellow oil (26 g, 97%). 1H-NMR (400 MHz, CDCl3) 7.16 (t, J=7.9 Hz, 1H), 7.84 (d, J=8.3 Hz, 1H), 6.79 (d, J=7.5 Hz, 1H), 3.84 (s, 3H), 3.73 (s, 2H), 3.05-3.01 (m, 2H), 2.55 (t, J=7.0 Hz, 2H), 2.01-1.96 (m, 2H). LC/MS (ESI+) m/z=191 (M+H)+

Workup

  1. filtrationThe solution was filtered
  2. customthe organics partitioned between dichloromethane and water
  3. dry with materialThe organics were dried (MgSO4)
  4. concentrationconcentrated
  5. customPurification by chromatography (ISCO, 330 g silica cartridge
  6. washstepwise elution hexane (5 min)

Sources & evidence

ORD record
ord-7037540766c84079bc7e2f1b9f8c4be0
Source dataset
uspto-grants-2016_05
Patent number
US09339502B2

Reaction notes

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