Chloroform → 2-Methoxy-8,9-dihydro-5H-benzo[7]annulen-6(7H)-one

HRID 2423647Notes

Reaction equation

HRID 2423647 reaction equation
[OH2:1].O.O.[N+]([O-])([O-])=O.[Tl+3].[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.[CH3:17][O:18][C:19]1[CH:20]=[C:21]2[C:26](=[CH:27][CH:28]=1)[C:25](=[CH2:29])[CH2:24][CH2:23][CH2:22]2.C(Cl)(Cl)Cl>CO>[CH3:17][O:18][C:19]1[CH:28]=[CH:27][C:26]2[CH2:25][C:29](=[O:1])[CH2:24][CH2:23][CH2:22][C:21]=2[CH:20]=1

Participants

5

Reactant 3

HCID 6212ChloroformHCID 11270721Nitric acid,thallium(3+) salt, trihydrate (9CI)HCID 123538226-Methoxy-1-methylene-1,2,3,4-tetrahydronaphthalene

Product 1

HCID 123691772-Methoxy-8,9-dihydro-5H-benzo[7]annulen-6(7H)-oneYield 91.6%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

The title compound was synthesized by referring to Tetrahedron Lett., 1977, 21, 1827. To a suspension of methyltriphenylphosphonium bromide (11.5 g) in tetrahydrofuran (50 ml) was added dropwise potassium tert-butoxide (1.0 M solution in tetrahydrofuran) (40 ml) on an ice bath under a nitrogen atmosphere, the solution was stirred for 1 hour, then a solution of 6-methoxy-1-tetralone (4.74 g) in tetrahydrofuran (26 ml) was added dropwise thereto followed by stirring for 2.5 hours at room temperature. Water was added thereto, the solution was stirred, extracted with ethyl acetate, then sequentially washed with water and brine, dried over anhydrous magnesium sulfate, and then the solvent was evaporated in vacuo. The residue was purified by silica gel column chromatography (hexane-ethyl acetate system) to provide 6-methoxy-1-methylene-1,2,3,4-tetrahydronaphthalene (4.4 g). To a solution of thallium(III) nitrate trihydrate (4.5 g) in methanol (40 ml) was added dropwise a solution of 6-methoxy-1-methylene-1,2,3,4-tetrahydronaphthalene (1.7 g) in methanol (13 ml) on an ice bath, and the solution was stirred for 10 minutes at room temperature. Chloroform was added thereto, the solution was stirred, then filtered through celite pad, extracted with diethyl ether, then sequentially washed with water and brine, dried over anhydrous magnesium sulfate, and then the solvent was evaporated in vacuo. The residue was purified by silica gel column chromatography (hexane-ethyl acetate system) to provide the title compound (1.7 g).

Workup

  1. stirringthe solution was stirred
  2. filtrationfiltered through celite pad
  3. extractionextracted with diethyl ether
  4. washsequentially washed with water and brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. customthe solvent was evaporated in vacuo
  7. customThe residue was purified by silica gel column chromatography (hexane-ethyl acetate system)

Sources & evidence

ORD record
ord-6b9c1becf10745a0b6f584f6be5dbc65
Source dataset
uspto-grants-2011_06
Patent number
US07960412B2

Reaction notes

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