Cesium carbonate → 3-Nitro-5-(2-oxopyrrolidin-1-yl)benzoic acid

HRID 852666Notes

Reaction equation

HRID 852666 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([N+:11]([O-:13])=[O:12])[CH:10]=1)[C:5]([OH:7])=[O:6].[C:14]([O-:17])([O-])=O.[Cs+].[Cs+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.O1CCOCC1>[N+:11]([C:9]1[CH:8]=[C:4]([CH:3]=[C:2]([N:11]2[CH2:9][CH2:8][CH2:4][C:14]2=[O:17])[CH:10]=1)[C:5]([OH:7])=[O:6])([O-:13])=[O:12]

Participants

6

Reactant 2

HCID 10796Cesium carbonateHCID 2393363-Bromo-5-nitrobenzoic acid

Product 1

HCID 222530233-Nitro-5-(2-oxopyrrolidin-1-yl)benzoic acidYield 148.7%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

A flask was charged under nitrogen with 3-bromo-5-nitro-benzoic acid (D5) (12.3 g, 50 mmol, 1 equiv), Cs2CO3 (24.4 g, 75 mmol, 1.5 equiv), tris(dibenzylideneacetone)dipalladium(0) (229 mg, 0.25 mmol, 0.005 equiv), Xantphos (433 mg, 0.75 mmol, 0.015 equiv) and dioxan (120 ml). 2-Pyrrolidin-2-one (5.7 ml, 75 mmol, 1.5 equiv) was then added via syringe and the resulting mixture was stirred at reflux for 60 h then cooled to room temperature and concentrated in vacuo. The residue was diluted with H2O and 1N aqueous NaOH solution and extracted twice with Et2O. The aqueous phase was then acidified to pH 1 and extracted three times with AcOEt. The combined organic phases were dried over MgSO4 and concentrated in vacuo to give 3-nitro-5-(2-oxo-pyrrolidin-1-yl)-benzoic acid (A27) (9.3 g, 75%) as a pale brown solid.

Workup

  1. temperatureat reflux for 60 h
  2. concentrationconcentrated in vacuo
  3. additionThe residue was diluted with H2O and 1N aqueous NaOH solution
  4. extractionextracted twice with Et2O
  5. extractionextracted three times with AcOEt
  6. dry with materialThe combined organic phases were dried over MgSO4
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-6cebce2ac16e40bd8e118f207827b04f
Source dataset
uspto-grants-2007_08
Patent number
US07253198B2

Reaction notes

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