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

HRID 2276302Notes

Reaction equation

HRID 2276302 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% dichloromethane (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-1d5dfea5e09945ed8f64588eb6bbe7f3
Source dataset
uspto-grants-2015_09
Patent number
US09132128B2

Reaction notes

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