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

HRID 1739142Notes

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>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.CN(C)C=O>[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-bromo-4-nitrobenzoic acid (0.50 g, 2.03 mmol) and 3,5-dimethylphenyl boronic acid (0.34 g, 2.23 mmol) were dissolved into anhydrous DMF (dimethylformamide) (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 into Et2O. It was dried over MgSO4 and the solvent was removed in vacuo. The crude material was chromatographed on silica gel using a 9:1 mixture of hexanes and ethyl acetate to yield 0.34 g (61.7%) of pure product. 1H NMR (CDCl3) 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) 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 into Et2O
dry with materialIt was dried over MgSO4
customthe solvent was removed in vacuo
customThe crude material was chromatographed on silica gel using
additiona 9:1 mixture of hexanes and ethyl acetate

Sources & evidence

ORD record: ord-70ec7d20e2ff4d19833962a302940f43
Source dataset: uspto-grants-1999_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05965539

Reaction notes

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