Hydrochloric Acid → 4-Ethynyl-4'-pentyl-1,1'-biphenyl

HRID 1386578Notes

Reaction equation

HRID 1386578 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.Cl.C(=O)([O-])[O-].[K+].[K+].N1CCC[CH2:28][CH2:27]1>ClCCl.CO.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.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(OCC)(=O)C.O>[CH2:14]([C:11]1[CH:12]=[CH:13][C:8]([C:5]2[CH:6]=[CH:7][C:2]([C:27]#[CH:28])=[CH:3][CH:4]=2)=[CH:9][CH:10]=1)[CH2:15][CH2:16][CH2:17][CH3:18]

Participants

11

Reactant 4

HCID 313Hydrochloric AcidHCID 8082PiperidineHCID 11430Potassium CarbonateHCID 6187094-Bromo-4'-pentylbiphenyl

Product 1

HCID 34468404-Ethynyl-4'-pentyl-1,1'-biphenyl

Reagents, catalysts & solvents 6

HCID 11776TriphenylphosphineCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 887MethanolSolventHCID 962WaterSolvent2×HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
90 °C

Procedure

A mixture of 4-bromo-4′-pentylbiphenyl (5.04 g), trimethylsilyacetylene (2.4 ml), tetrakis(triphenylphosphine)palladium (0.96 g), triphenylphosphine (0.22 g) and cuprous iodide (95 mg) in piperidine (10 ml) was heated for an hour under atmospheric pressure of nitrogen at 90° C. The reaction mixture was poured into a mixture of cold water and ethyl acetate, and adjusted to about pH 1 with 6N hydrochloric acid. The separated organic layer was washed with water and brine, and dried over magnesium sulfate. The magnesium sulfate was filtered of, and the filtrate was evaporated under reduced pressure to give crude 2-[4-(4-pentylphenyl)phenyl]-1-trimethylsilylacetylene, which was used for the next reaction without further purification. Crude mixture was dissolved in a mixture of dichloromethane (10 ml) and methanol (10 ml), and to the solution was added potassium carbonate (2.75 g) at 0° C. The mixture was allowed to warm to ambient temperature, and stirred for another 2 hours. The reaction mixture was poured into a mixture of cold water and ethyl acetate, and the resultant precipitate was filtered off. The filtrate was adjusted to about pH 7 with 1N hydrochloric acid, and washed with brine, and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the filtrate was evaporated under reduced pressure to give a crude powder, which was subjected to column chromatography on silica gel (300 ml), and eluted with a mixture of (n-hexane:ethyl acetate=99:1-97:3, V/V) to give 4-(4-Pentylphenyl)phenylacetylene (2.09 g).

Workup

  1. washThe separated organic layer was washed with water and brine
  2. dry with materialdried over magnesium sulfate
  3. filtrationThe magnesium sulfate was filtered of, and the filtrate
  4. customwas evaporated under reduced pressure
  5. customto give crude 2-[4-(4-pentylphenyl)phenyl]-1-trimethylsilylacetylene, which
  6. customwas used for the next reaction without further purification
  7. temperatureto warm to ambient temperature
  8. filtrationthe resultant precipitate was filtered off
  9. washwashed with brine
  10. dry with materialdried over magnesium sulfate
  11. filtrationThe magnesium sulfate was filtered off
  12. customthe filtrate was evaporated under reduced pressure
  13. customto give a crude powder, which
  14. washeluted with a mixture of (n-hexane:ethyl acetate=99:1-97:3, V/V)

Sources & evidence

ORD record
ord-663dff1bcdc8453fb0094ca363e08f59
Source dataset
uspto-grants-2001_07
Patent number
US06265536B1

Reaction notes

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