Trimethyl(3,4-methylenedioxy-6-nitrophenyl)stannane → 7-(4,5-Methylenedioxy-2-nitrophenyl)-2-methoxynaphthalene

HRID 1582893Notes

Reaction equation

HRID 1582893 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([CH:7]=[CH:8][C:9](OS(C(F)(F)F)(=O)=O)=[CH:10]2)=[CH:5][CH:4]=1.C[Sn](C)(C)[C:23]1[C:28]([N+:29]([O-:31])=[O:30])=[CH:27][C:26]2[O:32][CH2:33][O:34][C:25]=2[CH:24]=1>C1COCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:33]1[O:34][C:25]2[C:26](=[CH:27][C:28]([N+:29]([O-:31])=[O:30])=[C:23]([C:9]3[CH:10]=[C:11]4[C:6]([CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:12]4)=[CH:7][CH:8]=3)[CH:24]=2)[O:32]1

Participants

5

Reactant 2

HCID 10782610Trimethyl(3,4-methylenedioxy-6-nitrophenyl)stannaneHCID 10892112Methanesulfonic acid, trifluoro-, 7-methoxy-2-naphthalenyl ester

Product 1

HCID 227164227-(4,5-Methylenedioxy-2-nitrophenyl)-2-methoxynaphthaleneYield 34%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Tetrakis(triphenylphosphine)palladium (0) (120 mg) and cuprous bromide (20 mg) were added to a solution of 7-Methoxy-2-trifluoromethanesulfonyloxynaphthalene 47 (336 mg, 1.1 mmol) and trimethylnitroarylstannane 62 (300 mg, 0.92 mmol) in THF (30 mL) at room temperature and stirred for 0.5 h. The mixture was then refluxed under N2 overnight. After cooling, THF was evaporated in vacuo and ethyl acetate (30 mL) was added to the residue. The solution was washed with water. The organic layer was separated and passed through a Celite bed to remove suspended particles. The organic layer was then washed with brine, dried (anhydrous Na2SO4), and evaporated in vacuo. The residue was chromatographed using a 80:20 mixture of hexanes:ethyl acetate to give 48 (100 mg) in 34% yield; IR (KBr) 2915, 1627, 1509, 1481, 1425, 1333, 1262, 1218 cm−1; 1H NMR (CDCl3) δ3.92 (3H, s), 6.15 (2H, s), 6.88 (1H, s), 7.13-7.23 (3H, m), 7.48 (1H, s), 7.64 (1H, s), 7.74-7.81 (2H, m); 13C NMR δ55.81, 103.47, 105.90, 106.46, 111.60, 119.84, 124.13, 126.07, 128.50, 128.72, 129.75, 133.89, 134.97, 136.60, 143.42, 147.63, 151.45, 158.61; HRMS (EI) calcd for C18H13NO5 m/z: 323.0794; found: 323.0787.

Workup

  1. temperatureThe mixture was then refluxed under N2 overnight
  2. temperatureAfter cooling
  3. customTHF was evaporated in vacuo and ethyl acetate (30 mL)
  4. additionwas added to the residue
  5. washThe solution was washed with water
  6. customThe organic layer was separated
  7. customto remove
  8. washThe organic layer was then washed with brine
  9. dry with materialdried (anhydrous Na2SO4)
  10. customevaporated in vacuo
  11. customThe residue was chromatographed
  12. additiona 80:20 mixture of hexanes

Sources & evidence

ORD record
ord-84965191ddc641e893d486bff2090e79
Source dataset
uspto-grants-2004_05
Patent number
US06740650B2

Reaction notes

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