Hydrochloric Acid → 2-(3,5-Dimethylphenyl)-4-nitrobenzoic acid

HRID 325207Notes

Reaction equation

Br[C:2]1[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[CH3:14][C:15]1[CH:16]=[C:17](B(O)O)[CH:18]=[C:19]([CH3:21])[CH:20]=1.C([O-])([O-])=O.[Cs+].[Cs+].Cl>CN(C=O)C.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+:11]([C:9]1[CH:8]=[CH:7][C:3]([C:4]([OH:6])=[O:5])=[C:2]([C:17]2[CH:18]=[C:19]([CH3:21])[CH:20]=[C:15]([CH3:14])[CH:16]=2)[CH:10]=1)([O-:13])=[O:12]

Participants

Conditions

Temperature: 100 °C

Procedure

2-Bromo4-nitrobenzoic acid (0.43 g, 2.03 mmol) and 3,5-dimethylphenyl boronic acid (0.334 g, 2.23 mmol) were dissolved in anhydrous DMF (25 mL) under nitrogen. To this mixture was added Cs2CO3 (1.66 g, 5.08 mmol) followed by Pd(Ph3P)4 (0.12 g, 5%). The mixture was heated at 100° C. overnight. The solution was poured onto 1N HCl and extracted with Et2O. It was dried over MgSO4 and the solvent was removed in vacuo. The crude product was chromatographed on silica gel using a 9:1 mixture of hexanes and ethyl acetate to provide the desired product (0.34 g): 1H NMR (CDCl3) d 2.36 (6H, s), 6.99 (2H, s), 7.07 (1H, s), 8.03 (1H, d, J=9.0 Hz), 8.23-8.25 (2H, m); 13C NMR (CDCl3) d 21.28, 121.68, 123.68, 125.74, 126.07, 130.22, 131.19, 131.31, 135.04, 138.21, 144.74, 170.75.

Workup

extractionextracted with Et2O
dry with materialIt was dried over MgSO4
customthe solvent was removed in vacuo
customThe crude product was chromatographed on silica gel using
additiona 9:1 mixture of hexanes and ethyl acetate

Sources & evidence

ORD record: ord-176fd015fa844ff2b3feb625b368f773
Source dataset: uspto-grants-2001_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06221865B1

Reaction notes

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