Triethylamine → Benzoic acid, 2-(2-phenylethynyl)-, methyl ester

HRID 1186686Notes

Reaction equation

HRID 1186686 reaction equation
Br[C:2]1[CH:11]=[CH:10][CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].C(N(CC)CC)C.[C:19]1([C:25]#[CH:26])[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>C(#N)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>[C:19]1([C:25]#[C:26][C:2]2[CH:11]=[CH:10][CH:9]=[CH:8][C:3]=2[C:4]([O:6][CH3:7])=[O:5])[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 10821PhenylacetyleneHCID 11894Methyl 2-bromobenzoate

Product 1

HCID 10537767Benzoic acid, 2-(2-phenylethynyl)-, methyl esterYield 57.1%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
75 °C

Procedure

To a solution of methyl 2-bromobenzoate 34 (166 μL, 1.163 mmol) in acetonitrile (2906 μL) was added triethylamine (972 μL, 6.98 mmol) and phenylacetylene 35 (140 μl, 1.279 mmol). Then copper (I) iodide (11.07 mg, 0.058 mmol), and bis(triphenylphosphine)-palladium(II) chloride (20.40 mg, 0.029 mmol), were successively added, degassing between and after each addition of catalysts. The mixture was stirred at 75° C. overnight. The reaction mixture was partitioned between EtOAc and 1M HCl. The aqueous layer was extracted with fresh EtOAc and the combined organic layers were washed with water, brine, dried over MgSO4. The residue was purified via Biotage using EtOAc/Hex ((0:100 to 10:90); 25+S column), to afford compound 36 (157 mg, 57%). LRMS (ESI): (calc.) 236.08 (found) 237.2 (MH)+

Workup

  1. customdegassing between and
  2. additionafter each addition of catalysts
  3. customThe reaction mixture was partitioned between EtOAc and 1M HCl
  4. extractionThe aqueous layer was extracted with fresh EtOAc
  5. washthe combined organic layers were washed with water, brine
  6. dry with materialdried over MgSO4
  7. customThe residue was purified via Biotage

Sources & evidence

ORD record
ord-17153fa378904a07ad4d2e004a0d2f80
Source dataset
uspto-grants-2014_03
Patent number
US08673911B2

Reaction notes

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