Methyl 4-bromo-2-nitrobenzoate → 2-Nitro-4-vinyl-benzoic acid methyl ester

HRID 1441624Notes

Reaction equation

HRID 1441624 reaction equation
[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][C:7](Br)=[CH:6][C:5]=1[N+:11]([O-:13])=[O:12].[CH2:15](C([Sn])=C(CCCC)CCCC)[CH2:16]CC>O1CCOCC1.CCOC(C)=O.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>[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][C:7]([CH:15]=[CH2:16])=[CH:6][C:5]=1[N+:11]([O-:13])=[O:12]

Participants

6

Reactant 2

HCID 18350461Methyl 4-bromo-2-nitrobenzoateHCID 53438229Tri(butyl)vinyltin

Product 1

HCID 591644672-Nitro-4-vinyl-benzoic acid methyl esterYield 102.8%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 4-bromo-2-nitro-benzoic acid methyl ester (1 g, 3.85 mmol) in dioxane (5 mL) were added tributylvinyltin (1.7 mL, 5.76 mmol) and Pd(Ph3P)2Cl2 (275.4 mg, 0.385 mmol). The reaction mixture was stirred at 80° C. for 18 h, was cooled to r.t. and was diluted with EtOAc. After removal of the precipitate by filtration, the solution was concentrated in vacuo. The residue was purified by flash chromatography (silica gel, hexanes 1:1 hexanes:EtOAc) to provide the title compound (820 mg, 100%, 97% purity by HPLC) as a yellow oil. ESI-MS: m/z 208.2 [M+H]+, rt 5.14 min.

Workup

  1. temperaturewas cooled to r.t.
  2. customAfter removal of the precipitate
  3. filtrationby filtration
  4. concentrationthe solution was concentrated in vacuo
  5. customThe residue was purified by flash chromatography (silica gel, hexanes 1:1 hexanes:EtOAc)

Sources & evidence

ORD record
ord-7a76e81ad050402b963b34fccfd6ebbc
Source dataset
uspto-grants-2010_02
Patent number
US07655666B2

Reaction notes

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