Bromo-3-nitrobenzoic Acid

The reaction product from the mercuration of 3-nitro-phthalic acid (1 mole) is used. The mercury compound can be used without drying if desired. If this is done, solution takes place much more readily. 

A rapid distribution of the added material is necessary to prevent a local excess of the reagent added. This is very important when hydrochloric acid is added, as this tends to decompose the mercury compound. A convenient arrangement consists of a 3-way tube of about 15-mm. bore. The stirrer operates through the center tube. The other arms are used for the condenser and for the addition of material. A three-necked flask provided with a long-stemmed separatory funnel reaching below the stirrer may be used. 

The addition of one mole of hydrochloric acid allows the formation of one mole of sodium chloride, which is of advantage in the subsequent addition of halogen, owing to the formation of a sodium salt of the chloromercuric acid, this being more soluble and hence more reactive than the anhydro compound. Acetic 

The mercury can be replaced by iodine in a similar manner. An iodine solution is made by dissolving 166 g. (1 mole) of potassium iodide and 255 g. (1 mole) of iodine in 250 cc. of water. This is used instead of the bromine solution. The mixture is filtered from the mercuric iodide and the filtrate acidified with 200 cc. of concentrated hydrochloric acid. The precipitate is filtered and then stirred with a solution of 10 g. of potassium iodide in 250 cc. of water to remove mercuric iodide. The mixture is filtered with suction and the precipitate crystallized from 1 liter of 50 per cent alcohol. The yield is 180 g. of 2-iodo-3-nitrobenzoic acid melting at 204-205.50 (61 per cent of the theoretical amount, based on the 3-nitrophthalic acid used). 

2-Bromo-3-nitrobenzoic acid has been prepared by the nitration of 2-bromobenzoic acid, the 2,3 acid being separated from the 2,5 acid, which is the principal product of the nitration, by fractional crystallization of the potassium salts from water.1 

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The wet material may be used without drying for the preparation of 2-bromo-3-nitrobenzoic acid (p. 12). 

Ethyl 4-ctmino-3-nitrobenzoate mp 136° Insol in peer eth, sol in usual org solvents may be prepd by refluxing ethyl 4-bromo-3-nitrobenzoate and ale NH3 at 150° for 3 hrs by esterification of 4-amino 3 nitrobenzoic acid with abs ale in sulfuric acid or by refluxing ethyl 4 ethoxy-3-... 

Toluene Benzoic acid 3-Nitrobenzoic acid 3-Bromo-5-... 

C7H4BrN04 2-bromo-5-nitrobenzoic acid 943-14-6 25.00 1.8527 2 9760 C7H4CI4 1-chloro-2-(trichloromethyl)benzene 2136-89-2 20.00 1.5187 1... 

C7H4BrN04 4-bromo-3-nitrobenzoic acid 6319-40-0 25.00 1.8527 2 9762 C7H4CI4 1-chloro-4-(trichloromethyl)benzene 5216-25-1 20.00 1.4463 1... 

A range of simple analogs of benzoic acid and phenylalanine, easily obtainable from standard chemical suppliers, were chosen as substrates. These included a large number of hydroxy- and dihydroxybenzoic acids, aminoben-zoic acids, nitrobenzoic acids, fluoro-, difluoro-, trifluoro-, tetrafluoro- and pentafluorobenzoic acids, chlorobenzoic acids, iodobenzoic acids, and methoxybenzoic acids. A number of structures other than those with a six-mem-bered aromatic ring were also tried, including pyridinecarboxaldehydes, alicy-clic carboxylic acids, naphthalenecarboxylic acids, furancarboxylic acids, thiophenecarboxylic acids, nitro-, bromo-, and chlorothiophenecarboxyhc acids. 

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