Water → 6-Methoxy-1-methylene-1,2,3,4-tetrahydronaphthalene

HRID 2423646Notes

Reaction equation

HRID 2423646 reaction equation
[CH3:1]C(C)([O-])C.[K+].[CH3:7][O:8][C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[C:15](=[O:19])[CH2:14][CH2:13][CH2:12]2.O>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1>[CH3:7][O:8][C:9]1[CH:18]=[CH:17][C:16]2[CH2:1][C:15](=[O:19])[CH2:14][CH2:13][CH2:12][C:11]=2[CH:10]=1.[CH3:7][O:8][C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[C:15](=[CH2:1])[CH2:14][CH2:13][CH2:12]2

Participants

7

Reactant 3

HCID 962WaterHCID 141126-Methoxy-alpha-tetraloneHCID 23665647Potassium tert-butoxide

Product 2

HCID 123538226-Methoxy-1-methylene-1,2,3,4-tetrahydronaphthaleneHCID 123691772-Methoxy-8,9-dihydro-5H-benzo[7]annulen-6(7H)-one

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

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. stirringby stirring for 2.5 hours at room temperature
  2. stirringthe solution was stirred
  3. extractionextracted with ethyl acetate
  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-d698201044034b938c54c8e98e7e07fa
Source dataset
uspto-grants-2011_06
Patent number
US07960412B2

Reaction notes

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