2-Methyl-3-butyn-2-ol → HCID 22709077, compound

HRID 352265Notes

Reaction equation

HRID 352265 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][O:15][CH:16]2[CH2:21][CH2:20][CH2:19][CH2:18][O:17]2)=[CH:4][CH:3]=1.[CH3:22][C:23](O)(C#C)C>C(N(CC)CC)C.[Cu]I.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.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[O:17]1[CH2:18][CH2:19][CH2:20][CH2:21][CH:16]1[O:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][O:8][C:5]1[CH:6]=[CH:7][C:2]([C:22]#[CH:23])=[CH:3][CH:4]=1

Participants

7

Reactant 2

HCID 82582-Methyl-3-butyn-2-olHCID 22709078HCID 22709078, compound

Product 1

HCID 22709077HCID 22709077, compoundYield 72.5%

Reagents, catalysts & solvents 4

HCID 11776TriphenylphosphineCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

A degassed mixture of 4-bromo-1-[6-(tetrahydropyran-2-yloxy)hexyloxy]benzene (20 g), 2-methyl-3-butyn-2-ol (18.85 g), triphenylphosphine (TPP, 0.59 g), copper (I) iodide (0.11 g) and bis(triphenylphosphine)palladium dichloride (0.40 g) in 200 ml of triethylamine was refluxed for 4 hours under an atmosphere of argon. After being cooled the reaction mixture was filtered over celite to give a yellowish solution which was evaporated to dryness. The resulting yellow oil was dissolved in 200 ml of a toluene/triethylamine mixture (1:1) to which 14.45 g of KOH was then added. The resulting mixture was heated at reflux for 12 h, cooled and filtered over 260 g of silica gel using diethylether as eluent. This yields a dark oil which was purified by chromatography using a silica gel clolumn and cyclohexane/ethyl acetate (9:1) as eluent to give 12.28 g of 4-[6-(tetrahydropyran-2-yloxy)hexyloxy]phenylacetylene as a red oil.

Workup

  1. temperaturewas refluxed for 4 hours under an atmosphere of argon
  2. temperatureAfter being cooled the reaction mixture
  3. filtrationwas filtered over celite
  4. customto give a yellowish solution which
  5. customwas evaporated to dryness
  6. dissolutionThe resulting yellow oil was dissolved in 200 ml of a toluene/triethylamine mixture (1:1) to which 14.45 g of KOH
  7. additionwas then added
  8. temperatureThe resulting mixture was heated
  9. temperatureat reflux for 12 h
  10. temperaturecooled
  11. filtrationfiltered over 260 g of silica gel
  12. customThis yields a dark oil which
  13. customwas purified by chromatography

Sources & evidence

ORD record
ord-a3bc342d823e4692adcb9130157ec34a
Source dataset
uspto-grants-2004_06
Patent number
US06746729B1

Reaction notes

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