[N+]([O-])(O)=O.OS(O)(=O)=O.[CH3:10][C:11]1C=C(C=CC=1)C(O)=O.CC1C([N+]([O-])=O)=C(C([N+]([O-])=O)=CC=1)C(O)=O.[CH3:36][C:37]1[C:38]([N+:49]([O-:51])=[O:50])=[CH:39][C:40]([N+:46]([O-:48])=[O:47])=[C:41]([CH:45]=1)[C:42]([OH:44])=[O:43].O=S(Cl)Cl>CCO>[CH3:36][C:37]1[C:38]([N+:49]([O-:51])=[O:50])=[CH:39][C:40]([N+:46]([O-:48])=[O:47])=[C:41]([CH:45]=1)[C:42]([O:44][CH2:10][CH3:11])=[O:43]To a mixture of HNO3 (95%, 80 mL) and H2SO4 (98%, 80 mL) was slowly added 3-methylbenzic acid (50 g, 0.37 mol) at 0° C. After addition, the mixture was stirred below 30° C. for 1.5 hours. The mixture was then poured into ice-water and stirred for 15 min. The precipitate solid was filtered and washed with water to give a mixture of 3-methyl-2,6-dinitro-benzoic acid and 5-methyl-2,4-dinitrobenzoic acid (70 g, 84%). To a solution of this mixture (70 g, 0.31 mol) in EtOH (150 mL) was added dropwise SOCl2 (54 g, 0.45 mol). The mixture was heated at reflux for 2 h before being concentrated to dryness under reduced pressure. The residue was partitioned between EtOAc (100 mL) and aq. Na2CO3 (10%, 120 mL). The organic layer was washed with brine (50 mL), dried over Na2SO4, and concentrated to dryness to obtain ethyl 5-methyl-2,4-dinitrobenzoate (20 g), which was placed aside. The aqueous layer was acidified by HCl to pH 2˜3 and the precipitated solid was filtered, washed with water, and dried in air to give 3-methyl-2,6-dinitrobenzoic acid (39 g, 47%).
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