Stannane, tributyl(1-ethoxyethenyl)- → HCID 68430673, compound

HRID 2267007Notes

Reaction equation

HRID 2267007 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12](Br)=[C:11]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:10]=1[C:24]([F:27])([F:26])[F:25])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([Sn](CCCC)(CCCC)[C:33]([O:35]CC)=[CH2:34])CCC>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>[CH2:17]([O:16][C:11]1[C:10]([C:24]([F:27])([F:26])[F:25])=[C:9]([O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[CH:14]=[CH:13][C:12]=1[C:33](=[O:35])[CH3:34])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

5

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 68431145HCID 68431145, compound

Product 1

HCID 68430673HCID 68430673, compoundYield 60%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

Add tetrakis(triphenylphosphine)palladium (2.93 g, 2.54 mmol) to a solution of 1,3-bis-benzyloxy-4-bromo-2-trifluoromethyl-benzene (11.10 g, 25.4 mmol) and tributyl-(1-ethoxy-vinyl)-stannane (10.08 g, 27.92 mmol) in dioxane (250 mL) and stir. Purge reaction vessel with argon. Heat to 100° C. After 6 hours, cool to ambient temperature and concentrate under reduced pressure. Add 2N aqueous hydrochloric acid (50 mL), and tetrahydrofuran (200 mL) and stir. After 30 minutes add water and extract with ethyl acetate. Combine organic layers, dry with sodium sulfate, filter and concentrate under reduced pressure to yield a residue. Purify the residue by flash chromatography eluting with a gradient of 0-20% ethyl acetate:hexanes to yield the title compound as a clear oil (6.10 g, 60%): 1H NMR (CD3CN) δ 2.48 (s, 3H), 4.89 (s, 2H), 5.25 (s, 2H), 7.08 (d, 1H), 7.33-7.48 (m, 10H), 7.83 (d, 1H).

Workup

  1. customPurge
  2. customreaction vessel with argon
  3. temperaturecool to ambient temperature
  4. concentrationconcentrate under reduced pressure
  5. additionAdd 2N aqueous hydrochloric acid (50 mL), and tetrahydrofuran (200 mL)
  6. stirringstir
  7. additionAfter 30 minutes add water
  8. extractionextract with ethyl acetate
  9. dry with materialCombine organic layers, dry with sodium sulfate
  10. filtrationfilter
  11. concentrationconcentrate under reduced pressure
  12. customto yield a residue
  13. customPurify the residue by flash chromatography
  14. washeluting with a gradient of 0-20% ethyl acetate

Sources & evidence

ORD record
ord-c26eb743b6154ccb8756f7b9447a9ff2
Source dataset
uspto-grants-2010_12
Patent number
US07858646B2

Reaction notes

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