Tributylvinyltin → HCID 67170307, compound

HRID 1506346Notes

Reaction equation

HRID 1506346 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:24](=[CH:25][CH:26]=1)[C:8]1=[N:9][O:10][C:11]([C:12]3[CH:13]=[CH:14][C:15]([O:20][CH:21]([CH3:23])[CH3:22])=[C:16]([CH:19]=3)[C:17]#[N:18])=[C:7]1[CH2:6][CH2:5]2.[CH2:27]([Sn](CCCC)(CCCC)C=C)[CH2:28]CC.[Cl-].[Li+]>O1CCOCC1.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>[CH:21]([O:20][C:15]1[CH:14]=[CH:13][C:12]([C:11]2[O:10][N:9]=[C:8]3[C:24]4[C:4]([CH2:5][CH2:6][C:7]=23)=[CH:3][C:2]([CH:27]=[CH2:28])=[CH:26][CH:25]=4)=[CH:19][C:16]=1[C:17]#[N:18])([CH3:22])[CH3:23]

Participants

6

Reactant 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 67172060HCID 67172060, compound

Product 1

HCID 67170307HCID 67170307, compoundYield 67.3%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

5-(7-Bromo-4,5-dihydronaphtho[1,2-c]isoxazol-3-yl)-2-isopropoxybenzonitrile (Preparation 15B, 0.15 g, 0.367 mmol) dissolved in dioxane (3 mL) was transferred to a 15 mL sealed tube. Tributyl(vinyl)stannane (0.118 mL, 0.403 mmol) was added followed by lithium chloride (0.047 g, 1.100 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.042 g, 0.037 mmol). The contents were purged with nitrogen gas for 5 min., immersed in an oil bath, and heated at 100° C. for 14 h. The reaction mixture was concentrated and to the red-brown oil was added ethyl acetate (10 mL). The contents were sonicated for 5 min. and filtered. The filter cake was washed with ethyl acetate (2×5 mL). The filtrate was concentrated under reduced pressure and the resulting oil was subjected to silica gel column chromatography (hexane/ethyl acetate). Fractions corresponding to the product were collected and concentrated to yield 2-isopropoxy-5-(7-vinyl-4,5-dihydronaphtho[1,2-c]isoxazol-3-yl)benzonitrile (0.088 g, 0.247 mmol, 67% yield) as a pale yellow solid. LC/MS M+1=357.1.

Workup

  1. customsealed tube
  2. customThe contents were purged with nitrogen gas for 5 min.
  3. customimmersed in an oil bath
  4. concentrationThe reaction mixture was concentrated and to the red-brown oil
  5. additionwas added ethyl acetate (10 mL)
  6. customThe contents were sonicated for 5 min.
  7. filtrationfiltered
  8. washThe filter cake was washed with ethyl acetate (2×5 mL)
  9. concentrationThe filtrate was concentrated under reduced pressure
  10. customFractions corresponding to the product were collected
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-443dd8f591dd436ea1f952709998e32f
Source dataset
uspto-grants-2015_12
Patent number
US09216972B2

Reaction notes

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