Trimethylsilylacetylene → Methyl 3-hydroxy-4-[2-(trimethylsilyl)ethynyl]benzoate

HRID 2306658Notes

Reaction equation

HRID 2306658 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][C:11]=1I)[C:5]([O:7][CH3:8])=[O:6].[CH3:13][Si:14]([C:17]#[CH:18])([CH3:16])[CH3:15]>C1COCC1.C(Cl)(Cl)Cl.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>[OH:1][C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][C:11]=1[C:18]#[C:17][Si:14]([CH3:16])([CH3:15])[CH3:13])[C:5]([O:7][CH3:8])=[O:6]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 10378812Methyl 3-hydroxy-4-iodobenzoate

Product 1

HCID 22481756Methyl 3-hydroxy-4-[2-(trimethylsilyl)ethynyl]benzoateYield 91%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

Methyl 3-hydroxy-4-iodobenzoate (5.22 g, 18.8 mmol) is combined with trimethylsilylacetylene (3.71 mL, 26.3 mmol), bis(triphenylphosphine)palladium dichloride (386 mg, 0.55 mmol) and cuprous iodide (54 mg, 0.28 mmol) in THF (20 mL) CHCl3 (40 mL) in a dry flask, under nitrogen. TEA (8.14 mL<58.4 mmol) is added and the mixture is heated to 50° C. for 4 h. The mixture is diluted with CHCl3 (60 mL), washed with 5% HCl (2×40 mL), dried over anhydrous MgSO4 and concentrated to a brown paste (8.31 g). The crude material is chromatographed over a standard 90 g Biotage column, eluting with 10% EtOAc/hexane (1 L) followed by 15% EtOAc/hexane (1 L). The appropriate fractions are combined and concentrated to afford 4.22 g (91%) of methyl 3-hydroxy-4-[(trimethylsilyl)ethynyl]benzoate as a yellow solid. HRMS (FAB) calcd for C13H16O3SI+H1: 249.0947, found 249.0947.

Workup

  1. washwashed with 5% HCl (2×40 mL)
  2. dry with materialdried over anhydrous MgSO4
  3. concentrationconcentrated to a brown paste (8.31 g)
  4. customThe crude material is chromatographed over a standard 90 g Biotage column
  5. washeluting with 10% EtOAc/hexane (1 L)
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-c6a9b2be08e849c1a9885f6719c14938
Source dataset
uspto-grants-2004_12
Patent number
US06828330B2

Reaction notes

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