Stannane, tributyl(1-methylethenyl)- → 2-Chloro-4-isopropenyl-benzoic acid methyl ester

HRID 60561

Reaction equation

HRID 60561 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7](Br)=[CH:6][C:5]=1[Cl:11].[C:13]([Sn](CCCC)(CCCC)CCCC)([CH3:15])=[CH2:14]>C1COCC1>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([C:13]([CH3:15])=[CH2:14])=[CH:6][C:5]=1[Cl:11]

Participants

4

Reactant 2

HCID 10871254Stannane, tributyl(1-methylethenyl)-HCID 22058730Methyl 4-Bromo-2-chlorobenzoate

Product 1

HCID 669274782-Chloro-4-isopropenyl-benzoic acid methyl ester

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of 4-bromo-2-chlorobenzoic acid methyl ester (500 mg, 2 mmol) in THF (15 mL) was added isopropenyltributylstannane (700 mg, 2.1 mmol) and PdCl2(dppf)-2-DCM (165 mg, 0.2 mmol). The solution was heated to 60° C. for 12 hours. The crude reaction mixture was then concentrated down and taken up in 20 mL EtOAc and 100 mL concentrated KF solution. The reaction stirred at room temperature for 3 hours, filtered through a pad of celite and concentrated down. The residual oil was subjected to flash chromatography (Isco Companion, 40 g SiO2 cartridge, solid loaded SiO2, neat heptanes to EtOAc gradient) to give 2-chloro-4-isopropenyl-benzoic acid methyl ester as a yellow oil. Amount obtained: 230.6 mg (55%). LCMS (M/Z): 211 (M+H).

Workup

  1. customThe crude reaction mixture
  2. concentrationwas then concentrated down
  3. filtrationfiltered through a pad of celite
  4. concentrationconcentrated down

Sources & evidence

ORD record
ord-ff4cffabfd8144d49d757ba3c5c1f7c1
Source dataset
uspto-grants-2016_09
Patent number
US09440994B2

Linked notes

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