Tetrahydrofuran → 6-(4,5-Methylenedioxy-2-nitrophenyl)-2,3-dimethoxy-5-nitronaphthalene

HRID 1582895Notes

Reaction equation

HRID 1582895 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)=[C:10]2[N+:13]([O-:15])=[O:14])=[CH:5][CH:4]=1.C[Sn](C)(C)[C:26]1[C:31]([N+:32]([O-:34])=[O:33])=[CH:30][C:29]2[O:35][CH2:36][O:37][C:28]=2[CH:27]=1.C1C[O:43][CH2:42]C1>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>[CH2:36]1[O:37][C:28]2[C:29](=[CH:30][C:31]([N+:32]([O-:34])=[O:33])=[C:26]([C:9]3[C:10]([N+:13]([O-:15])=[O:14])=[C:11]4[C:6](=[CH:7][CH:8]=3)[CH:5]=[C:4]([O:43][CH3:42])[C:3]([O:2][CH3:1])=[CH:12]4)[CH:27]=2)[O:35]1

Participants

5

Reactant 3

HCID 8028TetrahydrofuranHCID 10782610Trimethyl(3,4-methylenedioxy-6-nitrophenyl)stannaneHCID 227164357-Methoxy-1-nitro-2-trifluoromethanesulfonyloxynaphthalene

Product 1

HCID 227164396-(4,5-Methylenedioxy-2-nitrophenyl)-2,3-dimethoxy-5-nitronaphthaleneYield 42%

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Procedure

Tetrakis(triphenylphosphine)palladium (0) (100 mg) and cuprous bromide (20 mg) was added to a solution of 7-Methoxy-1-nitro-2-trifluoromethanesulfonyloxy-naphthalene 53 (366 mg, 1.04 mmol) and trimethylnitroarylstannane 62 (500 mg, 1.52 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 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 70:30 mixture of hexanes:ethyl acetate to give 54 (160 mg) in 42% yield; mp 187-189° C.; IR (KBr) 2925, 1628, 1526, 1487, 1364, 1332, 1265, 1230 cm−1; 1H NMR (CDCl3) δ3.92 (3H, s), 6.19 (2H, d), 6.76 (1H, s), 7.12 (1H, d, J=2.5), 7.18 (1H, d, J=8.3), 7.28 (1H, dd, J1=9.0, J2=2.3), 7.70 (1H, s), 7.85 (1H, d, J=9.2), 7.93 (1H, d, J=8.4), 13C NMR δ56.08, 100.59, 103.93, 106.31, 110.70, 121.54, 124.07, 126.47, 128.71, 129.55, 130.33, 130.99, 131.23, 142.83, 148.92, 152.07, 160.68.

Workup

  1. temperatureThe mixture was then refluxed under N2 overnight
  2. temperatureAfter cooling
  3. customTHF was evaporated
  4. additionethyl acetate (30 mL) was 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 70:30 mixture of hexanes

Sources & evidence

ORD record
ord-dbe2ca84eeb44d59b0369fe900b84bdb
Source dataset
uspto-grants-2004_05
Patent number
US06740650B2

Reaction notes

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