Methanol → HCID 86633522, compound

HRID 2428076Notes

Reaction equation

HRID 2428076 reaction equation
C[Si]([C:5]#[CH:6])(C)C.FC(F)(F)C1C=CC([C:15]#[C:16][C:17]2[CH:18]=[C:19]([CH:34]=[C:35](C#CC3C=CC(C(F)(F)F)=CC=3)[CH:36]=2)[CH2:20][O:21][C:22]2[CH:32]=[CH:31][C:25]([O:26][CH2:27][C:28]([OH:30])=[O:29])=[C:24]([CH3:33])[CH:23]=2)=CC=1.[C:51](=O)([O-])[O-].[K+].[K+].CO>C(N(CC)CC)C.[Cu]I.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.ClCCl>[C:16]([C:17]1[CH:18]=[C:19]([CH:34]=[C:35]([C:5]#[CH:6])[CH:36]=1)[CH2:20][O:21][C:22]1[CH:32]=[CH:31][C:25]([O:26][CH2:27][C:28]([O:30][CH3:51])=[O:29])=[C:24]([CH3:33])[CH:23]=1)#[CH:15]

Participants

9

Reactant 4

HCID 887MethanolHCID 11430Potassium CarbonateHCID 66111TrimethylsilylacetyleneHCID 57826287HCID 57826287, compound

Product 1

HCID 86633522HCID 86633522, compound

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 6344DichloromethaneSolvent2×HCID 8471TriethylamineSolvent

Conditions

Temperature
70 °C

Procedure

Trimethylsilylacetylene (420 μL, 3.0 mmol) was added to a mixture of methyl [4-(3,5-dibromobenzyloxy)-2-methylphenoxy]acetate (444 mg, 1.0 mmol; prepared as described in example 15), copper(I) iodide (13 mg, 0.07 mmol) and tetrakis(triphenylphosphine)palladium (35 mg, 0.03 mmol) in dry triethylamine (8 mL). The reaction mixture was stirred for 3 h at 70° C. and then at ambient temperature overnight. The resulting mixture was evaporated in vacuo, the residue was dissolved in ether/ethyl acetate mixture (1:1, 20 mL) and the formed precipitate was filtered off. The filtrate was evaporated in vacuo to yield red-brown oil. Potassium carbonate (23 mg, 0.17 mmol), dry methanol (2 mL) and dry dichloromethane (2 mL) were added to the oil under nitrogen and the resulting mixture was stirred for 3 h. Dichloromethane (15 mL) was added and the mixture was washed with brine (15 mL). The aqueous layer was extracted with dichloromethane (2×10 mL); the combined organic layers were dried with anhydrous sodium sulfate and evaporated in vacuo. The crude product was purified by column chromatography (silica gel Fluka 60, hexanes/ethyl acetate 90:10-80:20) yielding methyl [4-(3,5-diethynylbenzyloxy)-2-methylphenoxy]acetate.

Workup

  1. customat ambient temperature
  2. customovernight
  3. customThe resulting mixture was evaporated in vacuo
  4. dissolutionthe residue was dissolved in ether/ethyl acetate mixture (1:1, 20 mL)
  5. filtrationthe formed precipitate was filtered off
  6. customThe filtrate was evaporated in vacuo
  7. customto yield red-brown oil
  8. stirringthe resulting mixture was stirred for 3 h
  9. washthe mixture was washed with brine (15 mL)
  10. extractionThe aqueous layer was extracted with dichloromethane (2×10 mL)
  11. dry with materialthe combined organic layers were dried with anhydrous sodium sulfate
  12. customevaporated in vacuo
  13. customThe crude product was purified by column chromatography (silica gel Fluka 60, hexanes/ethyl acetate 90:10-80:20)

Sources & evidence

ORD record
ord-2d66c5ee7fb141589ebbed0b7980b63f
Source dataset
uspto-grants-2011_06
Patent number
US07968723B2

Reaction notes

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