Methyl chloroformate → Methyl 3-(3-fluorophenyl)prop-2-ynoate

HRID 1280409Notes

Reaction equation

HRID 1280409 reaction equation
Br[C:2](Br)=[CH:3][C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([F:10])[CH:5]=1.C([Li])CCC.Cl[C:18]([O:20][CH3:21])=[O:19]>C1COCC1.C(=O)(O)[O-].[Na+]>[CH3:21][O:20][C:18](=[O:19])[C:2]#[C:3][C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([F:10])[CH:5]=1

Participants

6

Reactant 3

HCID 6586Methyl chloroformateHCID 225623361-(2,2-Dibromoethenyl)-3-fluorobenzeneHCID 178418339Butyllithium

Product 1

HCID 54395407Methyl 3-(3-fluorophenyl)prop-2-ynoateYield 110.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 516892Sodium BicarbonateSolvent

Procedure

To a stirred solution of 1-(2,2-dibromo-vinyl)-3-fluoro-benzene (23.8 g) in anhydrous THF (350 ml) cooled to −78° was added dropwise over 30 minutes, n-butyllithium (2.2 eq, 1.6M in hexanes). The mixture was stirred for a further 30 minutes at −78° before methyl chloroformate (11.6 g, 9.5 ml) was added and the resultant mixture allowed to warm to 0° for 1 hour before being diluted with 1:1 saturated aqueous sodium bicarbonate:ammonium chloride (100 ml) and extracted into ether (2×100 ml). The combined organic extract was washed with brine (25 ml), dried (Na2SO4) and evaporated to dryness to give the title compound as a brown oil (16.7 g, 100%).

Workup

  1. additionwas added dropwise over 30 minutes
  2. additionwas added
  3. temperatureto warm to 0° for 1 hour
  4. extractionammonium chloride (100 ml) and extracted into ether (2×100 ml)
  5. extractionThe combined organic extract
  6. washwas washed with brine (25 ml)
  7. dry with materialdried (Na2SO4)
  8. customevaporated to dryness

Sources & evidence

ORD record
ord-f0fb45e20bd54216a92a038f5a16ce54
Source dataset
uspto-grants-2002_09
Patent number
US06451794B1

Reaction notes

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