Triethylamine → Methyl 4-trimethylsilylethynylbenzoate

HRID 928910Notes

Reaction equation

HRID 928910 reaction equation
[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][C:7](Br)=[CH:6][CH:5]=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[C:31]([Si:33]([CH3:36])([CH3:35])[CH3:34])#[CH:32].CCN(CC)CC>C1COCC1.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.CCOC(C)=O>[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][C:7]([C:32]#[C:31][Si:33]([CH3:36])([CH3:35])[CH3:34])=[CH:6][CH:5]=1

Participants

9

Reactant 4

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 12081Methyl 4-bromobenzoateHCID 66111Trimethylsilylacetylene

Product 1

HCID 640161Methyl 4-trimethylsilylethynylbenzoateYield 54%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

4-Bromobenzoic acid methyl ester (1.124 g, 5.22 mmol), PdCl2(PPh3)2 (192 mg, 27.4 mmol), and PPh3 (37 mg, 14.1 mmol) were suspended in THF (25.0 mL). Ethynyltrimethylsilane (1.14 mL, 8.1 mmol) and Et3N (1.14 mL, 7.8 mmol) were added and the reaction was allowed to stir for 20 min. CuI (14 mg, 0.075 mmol) was added and the reaction color changed from orange to red. Reaction was allowed to proceed overnight. After overnight reaction, the solution was brown in color and TLC analysis indicated the reaction was complete. The reaction mixture was concentrated to a brown residue, redissolved in DCM and filtered through Celite. The filtrate and rinses were evaporated to dryness and purification via Silica in 15:1 cyclohexane: EtOAc afforded 4-(trimethylsilyl)ethynyl-benzoic acid methyl ester (656 mg, 2.82 mmol, 54%) as an orange solid. H-NMR (CD3C1, 500 MHz) δ (ppm): 0.239 (s, 9H); 3.89 (s, 3H); 7.49 (d, J=16.84 Hz, 2H); 7.94 (d, J=16.4 Hz, 2H).

Workup

  1. customReaction
  2. waitto proceed overnight
  3. customAfter overnight reaction
  4. concentrationThe reaction mixture was concentrated to a brown residue
  5. dissolutionredissolved in DCM
  6. filtrationfiltered through Celite
  7. customThe filtrate and rinses were evaporated to dryness and purification via Silica in 15:1 cyclohexane

Sources & evidence

ORD record
ord-ef5c0bf0fd86430ba26d55bcb2beb842
Source dataset
uspto-grants-2016_03
Patent number
US09290791B2

Reaction notes

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