Tetrabutylammonium Fluoride → Methyl 2-chloro-4-ethynylbenzoate

HRID 1877424Notes

Reaction equation

HRID 1877424 reaction equation
[CH3:1][O:2][C:3](=[O:17])[C:4]1[CH:9]=[CH:8][C:7]([C:10]#[C:11][Si](C)(C)C)=[CH:6][C:5]=1[Cl:16].[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C1COCC1>[CH3:1][O:2][C:3](=[O:17])[C:4]1[CH:9]=[CH:8][C:7]([C:10]#[CH:11])=[CH:6][C:5]=1[Cl:16]

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 673682802-Chloro-4-trimethylsilanylethynyl-benzoic acid methyl ester

Product 1

HCID 71306162Methyl 2-chloro-4-ethynylbenzoateYield 48%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 2-chloro-4-trimethylsilanylethynyl-benzoic acid methyl ester (4.52 g, 12.0 mmol, 1.0 equiv; 70% purity) in THF (50 mL) was as added a 1 M solution of tetrabutylammonium fluoride in THF (14.4 mL, 14.40 mmol, 1.20 equiv; [CAS RN 429-41-4]) and the reaction mixture stirred at rt over night. The crude reaction was extracted from a sat. solution of NH4Cl (50 mL) with ethyl acetate (3×50 mL) and the combined organic phases dried over Na2SO4. Purification of the crude reaction product by silica column chromatography using a MPLC system (CombiFlash Companion, Isco Inc.) eluting with a mixture of dichloromethane/methanol (4:1) provided 1.12 g (48%) of the title compound as a slightly orange solid. MS (ISN): 195.1 [M+H]+.

Workup

  1. customThe crude reaction
  2. extractionwas extracted from a sat. solution of NH4Cl (50 mL) with ethyl acetate (3×50 mL)
  3. dry with materialthe combined organic phases dried over Na2SO4
  4. customPurification of the crude
  5. customreaction product by silica column chromatography
  6. washeluting with a mixture of dichloromethane/methanol (4:1)

Sources & evidence

ORD record
ord-5ac9166e8284401781eb161b08d9a056
Source dataset
uspto-grants-2012_11
Patent number
US08309734B2

Reaction notes

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