Potassium Carbonate → Methyl 4-nitro-2-vinylbenzoate

HRID 514274Notes

Reaction equation

HRID 514274 reaction equation
Br[C:2]1[CH:11]=[C:10]([N+:12]([O-:14])=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].C(=O)([O-])[O-].[K+].[K+].[CH:21](B1OB(C=C)OB(C=C)O1)=[CH2:22]>COCCOC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[N+:12]([C:10]1[CH:9]=[CH:8][C:3]([C:4]([O:6][CH3:7])=[O:5])=[C:2]([CH:21]=[CH2:22])[CH:11]=1)([O-:14])=[O:13]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 2734807TrivinylboroxinHCID 15833211Methyl 2-Bromo-4-nitrobenzoate

Product 1

HCID 57663378Methyl 4-nitro-2-vinylbenzoateYield 47.1%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent2×HCID 80711,2-DimethoxyethaneSolvent

Procedure

12.0 g (46.1 mmol) of methyl 2-bromo-4-nitrobenzoate were initially charged in 240 ml of 1,2-dimethoxyethane, 2.66 g (2.30 mmol) of tetrakis(triphenylphosphine)palladium were added, and the mixture was stirred for 20 min. Subsequently, a solution of 6.38 g (46.1 mmol) of potassium carbonate in 80 ml of water and 11.11 g (46.1 mmol) of 2,4,6-trivinylcyclotriboroxane were added. The reaction mixture was stirred at reflux temperature for 20 hours. After cooling, the mixture was added to water and extracted with ethyl acetate, the organic phases were dried with magnesium sulphate, and the solvent was distilled off under reduced pressure. The residue was chromatographed using silica gel with cyclohexane/ethyl acetate (ratio 6:1) as the eluent. 4.5 g (46% of theory) of methyl 4-nitro-2-vinylbenzoate were obtained.

Workup

  1. stirringThe reaction mixture was stirred
  2. temperatureat reflux temperature for 20 hours
  3. temperatureAfter cooling
  4. extractionextracted with ethyl acetate
  5. dry with materialthe organic phases were dried with magnesium sulphate
  6. distillationthe solvent was distilled off under reduced pressure
  7. customThe residue was chromatographed

Sources & evidence

ORD record
ord-aaa347896b754c61a5b2f5e6c69cc3e9
Source dataset
uspto-grants-2015_08
Patent number
US09107411B2

Reaction notes

Loading…