1,2-Benzenedicarboxylic acid, 3-nitro-, 1,2-dimethyl ester → HCID 358344, compound

HRID 1758790Notes

Reaction equation

HRID 1758790 reaction equation
[N+]([C:4]1[CH:13]=[CH:12][CH:11]=[C:6]([C:7]([O:9]C)=[O:8])[C:5]=1[C:14]([O:16][CH3:17])=[O:15])([O-])=O.[CH3:18][O-:19].[Na+]>CN(C)P(=O)(N(C)C)N(C)C.O>[C:14]([C:5]1[C:4]([O:19][CH3:18])=[CH:13][CH:12]=[CH:11][C:6]=1[C:7]([OH:9])=[O:8])([O:16][CH3:17])=[O:15]

Participants

5

Reactant 2

HCID 2499121,2-Benzenedicarboxylic acid, 3-nitro-, 1,2-dimethyl esterHCID 10942334Sodium Methoxide

Product 1

HCID 358344HCID 358344, compoundYield 77.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 12679HexamethylphosphoramideSolvent

Procedure

Dimethyl 3-nitrophthalate (4.8 g, 20 mmol) was added to a cold solution of sodium methoxide (2.61 g, 48.3 mmol) in dry hexamethylphosphoric triamide (75 ml). The resulting dark solution was gradually brought to room temperature and the reaction mixture was stirred for 44 hrs. It was then diluted with water (125 ml) and extracted with benzene. (This extract contained a variable quantity of dimethyl 3-methoxyphthalate. The aqueous layer was acidified with hydrochloric acid and extracted with benzene. The combined organic layers were washed with water (5×30 ml) and then brine (1×15 ml), dried over sodium sulfate, filtered and evaporated to give 3.25 g (75%) of 2-carbomethoxy-3-methoxybenzoic acid, mp 140°-141° C. (benzene). Identity was confirmed by mixture mp, co-chromatography and spectroscopic comparison with an authentic sample. 1H NMR (CDCl3) δ 3.86 (3H, s, ArCO2CH3), 3.93 (3H, s, ArOCH3), 7.13 (1H, dd, J=8,2 Hz, ArH4), 7.43 (1H, t, J=8 Hz, ArH5), 7.68 (1H, dd, J=8,2 Hz, ArH6, 10.50 (1H, broad s, ArCO2H); IR (KBr) 3200 (br), 2960, 1740, 1690, 1585, 1475, 1310, 1050 cm-1 , etc.; mass spectrum m/e (rel. intensity) 211 (m+ +1,5%), 210 M+, 30%), 193 (M+ -OH, 2%), 180 (M+ -2CH3, 100%), 179 (M+ -OCH3, 10%), etc.

Workup

  1. customwas gradually brought to room temperature
  2. extractionextracted with benzene
  3. extractionextracted with benzene
  4. washThe combined organic layers were washed with water (5×30 ml)
  5. dry with materialbrine (1×15 ml), dried over sodium sulfate
  6. filtrationfiltered
  7. customevaporated

Sources & evidence

ORD record
ord-77861ec520e3443eac2a06a3313b04df
Source dataset
uspto-grants-1983_02
Patent number
US04374979

Reaction notes

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