Trimethylsilylacetylene → HCID 18761562, compound

HRID 1282320Notes

Reaction equation

HRID 1282320 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([C:16]([CH3:19])([CH3:18])[CH3:17])=[C:6]([O:8][C:9]2[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][CH:10]=2)[CH:7]=1.[CH3:20][Si:21]([C:24]#[CH:25])([CH3:23])[CH3:22]>C(N(CC)CC)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:16]([C:5]1[CH:4]=[CH:3][C:2]([C:25]#[C:24][Si:21]([CH3:23])([CH3:22])[CH3:20])=[CH:7][C:6]=1[O:8][C:9]1[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][CH:10]=1)([CH3:19])([CH3:18])[CH3:17]

Participants

5

Reactant 2

HCID 66111Trimethylsilylacetylene2×HCID 69969167HCID 69969167, compound2×

Product 1

HCID 18761562HCID 18761562, compound

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalyst2×HCID 8471TriethylamineSolvent

Conditions

Temperature
75 °C

Procedure

In a sealed tube vessel, a solution of 323 mg (1.0 mmol) of 5-bromo-2-tert-butyl-1-[(4′-methyl)phenoxy]benzene (Compound J) in 6 mL of triethylamine was sparged (with a stream of argon bubbled vigorously into the solution) for several minutes. To this solution was added 48 mg (0.25 mmol) of cuprous iodide and the resultant mixture was sparged with argon for several minutes. To this reaction mixture was then added 175 mg (0.25 mmol) of bis(triphenylphosphine)palladium(II) chloride. After sparging with argon for a couple of minutes, 1.1 mL (1.0 g, 10.1 mmol) of trimethylsilyl acetylene was added to the reaction mixture. The pressure tube was then sealed and heated in an oil bath (75° C.) for 3 days at which time an additional 178 mg (0.25 mmol) of bis(triphenylphosphine)palladium(II) chloride and 1.0 mL (0.9 g, 9.4 mmol) of trimethylsilyl acetylene were added. The reaction mixture was heated at 75° C. for 4 days, filtered through celite and washed with ethyl ether (100 mL). The filtrate was extracted with water (3×75 mL-portions) and brine, dried over MgSO4, filtered and concentrated in vacuo to give a dark brown oil residue. Purification by flash chromatography (preabsorbed onto silica with 100% chloroform, eluted with 100% hexane) gave the title compound as a clear, colorless oil which solidified to a white solid.

Workup

  1. custombubbled vigorously into the solution) for several minutes
  2. customthe resultant mixture was sparged with argon for several minutes
  3. customAfter sparging with argon for a couple of minutes
  4. customThe pressure tube was then sealed
  5. additionwere added
  6. filtrationfiltered through celite
  7. washwashed with ethyl ether (100 mL)
  8. extractionThe filtrate was extracted with water (3×75 mL-portions) and brine
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customto give a dark brown oil residue
  13. customPurification
  14. customby flash chromatography (preabsorbed onto silica with 100% chloroform, eluted with 100% hexane)

Sources & evidence

ORD record
ord-fe529979c76949e29a19fd3984cf079a
Source dataset
uspto-grants-2002_09
Patent number
US06455701B1

Reaction notes

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