Tributylvinyltin → 3-(4-Propylphenyl)-7-vinyl-4,5-dihydronaphtho[1,2-c]isoxazole

HRID 1506338Notes

Reaction equation

HRID 1506338 reaction equation
FC(F)(S(O[C:17]1[CH:18]=[C:19]2[C:36](=[CH:37][CH:38]=1)[C:23]1=[N:24][O:25][C:26]([C:27]3[CH:32]=[CH:31][C:30]([CH2:33][CH2:34][CH3:35])=[CH:29][CH:28]=3)=[C:22]1[CH2:21][CH2:20]2)(=O)=O)C(F)(F)C(F)(F)C(F)(F)F.[Cl-].[Li+].[CH2:42]([Sn](CCCC)(CCCC)C=C)[CH2:43]CC>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.O1CCOCC1>[CH2:33]([C:30]1[CH:31]=[CH:32][C:27]([C:26]2[O:25][N:24]=[C:23]3[C:36]4[C:19]([CH2:20][CH2:21][C:22]=23)=[CH:18][C:17]([CH:42]=[CH2:43])=[CH:38][CH:37]=4)=[CH:28][CH:29]=1)[CH2:34][CH3:35]

Participants

6

Reactant 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 86669877HCID 86669877, compound

Product 1

HCID 671721833-(4-Propylphenyl)-7-vinyl-4,5-dihydronaphtho[1,2-c]isoxazoleYield 86.4%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

To a mixture of 3-(4-propylphenyl)-4,5-dihydronaphtho[1,2-c]isoxazol-7-yl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (Preparation 11A, 160 mg, 0.272 mmol), anhydrous lithium chloride (34.6 mg, 0.817 mmol), tributyl(vinyl)tin (0.120 mL, 0.409 mmol), and anhydrous dioxane (1 mL) was bubbled nitrogen gas for 3 min before Pd(Ph3P)4 (62.9 mg, 0.054 mmol) was added. The reaction mixture was purged with nitrogen gas for an additional 3 min, stirred for 1 h at room temperature, and then at 110° C. for 4 h. The reaction mixture was cooled and treated with saturated aqueous sodium bicarbonate solution (1.5 mL). The biphasic mixture was extracted with ethyl acetate (2×2 mL). The combined ethyl acetate extracts were dried over sodium sulfate and concentrated under reduced pressure. The residue was dissolved in dichloromethane and filtered through a pad of silica gel and rinsed with dichloromethane. The filtrate was concentrated to give 3-(4-propylphenyl)-7-vinyl-4,5-dihydronaphtho[1,2-c]isoxazole (74 mg, 0.235 mmol, 86% yield) LC/MS M+1=316.17.

Workup

  1. additionwas added
  2. customThe reaction mixture was purged with nitrogen gas for an additional 3 min
  3. waitat 110° C. for 4 h
  4. temperatureThe reaction mixture was cooled
  5. additiontreated with saturated aqueous sodium bicarbonate solution (1.5 mL)
  6. extractionThe biphasic mixture was extracted with ethyl acetate (2×2 mL)
  7. dry with materialThe combined ethyl acetate extracts were dried over sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. dissolutionThe residue was dissolved in dichloromethane
  10. filtrationfiltered through a pad of silica gel
  11. washrinsed with dichloromethane
  12. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-9767ff00f4894a2cade111cacb7d54f3
Source dataset
uspto-grants-2015_12
Patent number
US09216972B2

Reaction notes

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