Triethylamine → 4-[3,5-Di(trifluoromethyl)phenylethynyl]cyclohexanone

HRID 727190Notes

Reaction equation

HRID 727190 reaction equation
[C:1]([CH:3]1[CH2:12][CH2:11][C:6]2([O:10]CCO2)[CH2:5][CH2:4]1)#[CH:2].[F:13][C:14]([F:27])([F:26])[C:15]1[CH:16]=[C:17](I)[CH:18]=[C:19]([C:21]([F:24])([F:23])[F:22])[CH:20]=1.C(N(CC)CC)C>C(#N)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.[Cu]I>[F:13][C:14]([F:26])([F:27])[C:15]1[CH:16]=[C:17]([C:2]#[C:1][CH:3]2[CH2:4][CH2:5][C:6](=[O:10])[CH2:11][CH2:12]2)[CH:18]=[C:19]([C:21]([F:22])([F:23])[F:24])[CH:20]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 6309701-Iodo-3,5-bis(trifluoromethyl)benzeneHCID 197052738-Ethynyl-1,4-dioxaspiro[4.5]decane

Product 1

HCID 197052544-[3,5-Di(trifluoromethyl)phenylethynyl]cyclohexanone

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6342AcetonitrileSolvent

Procedure

A solution of 3.9 grams (0.022 mole) of 8-ethynyl-1,4-dioxaspiro[4.5]decane, 10.5 grams (0.031 mole) of 3,5-di(trifluoromethyl)phenyl iodide (prepared in Step A of this Example), 10.7 grams (0.077 mole) of triethylamine, 0.5 gram (catalyst) of bis(triphenylphosphine)palladium(II) chloride, and 0.5 gram (catalyst) of copper(I) iodide in 100 mL of acetonitrile is stirred at ambient temperature for about 18 hours. After this time the reaction mixture is concentrated under reduced pressure to a residue. The residue is then stirred for about 2 hours with 150 mL of aqueous 1N hydrochloric acid. After this time the mixture is extracted with three 100 mL portions of ethyl acetate. The combined extracts are washed with an aqueous solution of 10% lithium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding 4-[3,5-di(trifluoromethyl)phenylethynyl]cyclohexanone.

Workup

  1. concentrationAfter this time the reaction mixture is concentrated under reduced pressure to a residue
  2. stirringThe residue is then stirred for about 2 hours with 150 mL of aqueous 1N hydrochloric acid
  3. extractionAfter this time the mixture is extracted with three 100 mL portions of ethyl acetate
  4. washThe combined extracts are washed with an aqueous solution of 10% lithium chloride
  5. dry with materialThe organic layer is dried with magnesium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate is concentrated under reduced pressure

Sources & evidence

ORD record
ord-490946760c004400add7ed9f518badf6
Source dataset
uspto-grants-1998_01
Patent number
US05712281

Reaction notes

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