Trimethylsilylacetylene → 4,4-Dimethyl-7-((trimethylsilyl)ethynyl)-3,4-dihydronaphthalen-1(2H)-one

HRID 618020Notes

Reaction equation

HRID 618020 reaction equation
[CH3:1][C:2]1([CH3:14])[C:11]2[C:6](=[CH:7][C:8](Br)=[CH:9][CH:10]=2)[C:5](=[O:13])[CH2:4][CH2:3]1.[CH3:15][Si:16]([C:19]#[CH:20])([CH3:18])[CH3:17]>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>[CH3:15][Si:16]([C:19]#[C:20][C:8]1[CH:7]=[C:6]2[C:11]([C:2]([CH3:14])([CH3:1])[CH2:3][CH2:4][C:5]2=[O:13])=[CH:10][CH:9]=1)([CH3:18])[CH3:17]

Participants

5

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 107533577-Bromo-4,4-dimethyl-1,2,3,4-tetrahydronaphthalen-1-one2×

Product 1

HCID 106121314,4-Dimethyl-7-((trimethylsilyl)ethynyl)-3,4-dihydronaphthalen-1(2H)-one

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

To a solution (flushed for 15 minutes with a stream of argon) of 7 g (27.6 mmol) of 3,4-dihydro-4,4-dimethyl-7-bromo-1(2H)-naphthalenone (Compound B) in 150 ml of triethylamine was added 0.97 g (1.3 mmol) of bis(triphenylphosphine)palladium(II) chloride and 0.26 g (1.3 mmol) of cuprous iodide. The solution mixture was flushed with argon for 5 minutes and then 39 ml (36.6 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 7-(trimethylsilyl)ethynyl-3,4-dihydro-4,4-dimethylnaphthalen-1(2H)-one. To a solution of this crude TMS-acetylenic compound in 50 ml of methanol was added 0.6 g (4.3 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, washed with water, 10% HCl and brine, dried over MgSO4 and concentrated in vacuo. Purification by column chromatography (silica, 10% EtOAc-hexane) yielded the title compound as a white solid. PMR (CDCl3): δ 1.39 (6H, s), 2.02 (2H, t, J=7.0 Hz), 2.73 (2H, t, J=7.0 Hz), 3.08 (1H, s), 7.39 (1H, d, J=8.2 Hz), 7.61 (1H, dd, J=1.8, 8.2 Hz), 8.14 (1H, d, J=9 1.8 Hz).

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

Sources & evidence

ORD record
ord-865e1de30de24d9e94b570d2dce3a929
Source dataset
uspto-grants-1999_09
Patent number
US05952345

Reaction notes

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