Potassium Carbonate → 6-ethynyl-3,4-dihydro-4,4-dimethylnaphthalen-1(2H)-one

HRID 1216

Reaction equation

HRID 1216 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8](=[O:12])[CH2:7][CH2:6][C:5]2([CH3:14])[CH3:13].C[Si]([C:19]#[CH:20])(C)C.C([O-])([O-])=O.[K+].[K+]>C(N(CC)CC)C.CO.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:19]([C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8](=[O:12])[CH2:7][CH2:6][C:5]2([CH3:14])[CH3:13])#[CH:20]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 66111TrimethylsilylacetyleneHCID 118319356-Bromo-4,4-dimethyl-3,4-dihydronaphthalen-1(2H)-one2×

Product 1

HCID 225688236-ethynyl-3,4-dihydro-4,4-dimethylnaphthalen-1(2H)-one

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 887MethanolSolventHCID 8471TriethylamineSolvent

Procedure

To a solution (flushed for 15 minutes with a stream of argon) of 13.55 g (53.8 mmol) of 6-bromo-3,4-dihydro-4,4-dimethylnaphthalen-1(2H)-one (Compound H) in 280 ml of triethylamine was added 1.87 g (2.66 mmol) of bis(triphenylphosphine)palladium(II) chloride and 0.53 g (2.66 mmol) of cuprous iodide. The solution mixture was flushed with argon for 5 minutes and then 100 ml (938.7 mmol) of trimethylsilyl acetylene was added. The reaction mixture was sealed in a pressure tube and placed in a preheated oil bath (100° C.) for 24 hours. The reaction mixture was then filtered through celite, washed with Et2O and the filtrate concentrated in vacuo to give crude 6-(2-trimethylsilyl)ethynyl-3,4-dihydro-4,4-di-methyl-naphthalen-1(2H)-one. To a solution of this crude TMS-acetylenic compound in 50 ml of methanol was added 2.8 g (20.3 mmol) of K2CO3. The mixture was stirred for 8 hours at ambient temperature and then filtered. The filtrate was concentrated in vacuo, diluted with Et2O (100 ml), washed with water (10 ml), 10% HCl (10 ml) and brine (10 ml), dried over MgSO4 and concentrated in vacuo. Purification by column chromatography (silica, 10% EtOAc-hexane) yielded the title compound as a white solid.

Workup

  1. customThe solution mixture was flushed with argon for 5 minutes
  2. customThe reaction mixture was sealed in a pressure tube
  3. customplaced in a preheated oil bath
  4. filtrationThe reaction mixture was then filtered through celite
  5. washwashed with Et2O
  6. concentrationthe filtrate concentrated in vacuo
  7. customto give crude 6-(2-trimethylsilyl)ethynyl-3,4-dihydro-4,4-di-methyl-naphthalen-1(2H)-one
  8. filtrationfiltered
  9. concentrationThe filtrate was concentrated in vacuo
  10. additiondiluted with Et2O (100 ml)
  11. washwashed with water (10 ml), 10% HCl (10 ml) and brine (10 ml)
  12. dry with materialdried over MgSO4
  13. concentrationconcentrated in vacuo
  14. customPurification by column chromatography (silica, 10% EtOAc-hexane)

Sources & evidence

ORD record
ord-5100f97ff6524472837ccd21fd6bb444
Source dataset
uspto-grants-1998_03
Patent number
US05723620

Linked notes

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