5- Bromo-2-toluic acid

CH3. C6HBr(N02)2, CO.N3 C8BrH4Ns05 mw 330.07 N 21.22% OB to C02 -63.02% ndles (from a mixt of benz plus gasoline) mp 101°. Prepn is by reaction of 3,5-dinitro-2-bromo-toluic acid with Na azide in aq acet. The azide explds when heated rapidly Ref Beil 9, [335]... 

Both acid chlorides, including ethylsuccinyl chloride," and acid anhydrides "-" have been used as acylating agents, as have carbamoyl chlorides. Silver-assisted reactions of anhydrides of a-bromo-toluic acid also lead to alkynic ketones, probably via an intermediate acyloxyalkyloxycarbenium salt (Scheme 26). ... 

Clark, Am. Chem. J., 1892, 14, 669. ca-Bromo- toluic Acid o-Bromomethyl-benzoic acid, benzyl bromide o-earboxyUc add)... 

Pyridone IV was converted to its sodium salt by treatment with an equimolar amount of sodium methoxide in methanol (see procedure below under formation of the 3-phenyl-2(lH)pyridone sulfonates). The sodium salt was next treated with the methyl ester of a-bromo-p-toluic acid, obtained by treatment of the acid with BF3 etherate. 

A variety of cleavage conditions have been reported for the release of amines from a solid support. Triazene linker 52 prepared from Merrifield resin in three steps was used for the solid-phase synthesis of aliphatic amines (Scheme 22) [61]. The triazenes were stable to basic conditions and the amino products were released in high yields upon treatment with mild acids. Alternatively, base labile linker 53 synthesized from a-bromo-p-toluic acid in two steps was used to anchor amino functions (Scheme 23) [62]. Cleavage was accomplished by oxidation of the thioether to the sulfone with m-chloroperbenzoic acid followed by 13-elimination with a 10% solution of NH4OH in 2,2,2-trifluoroethanol. A linker based on l-(4,4 -dimethyl-2,6-dioxocyclohexylidene)ethyl (Dde) primary amine protecting group was developed for attaching amino functions (Scheme 24) [65]. Linker 54 was stable to both acidic and basic conditions and the final products were cleaved from the resin by treatment with hydrazine or transamination with ra-propylamine. 

For the synthesis of isoindoles (benzo[c]pyrroles) by type la cyclization the required intermediate is an o -acylbenzylamine. The only viable route to these substances which has been developed starts with a -bromo-o -toluic acid which is converted first to a phthalimide and then to the acid chloride. The acid chloride is then elaborated to the requisite ketone by Friedel-Crafts acylation. Condensation to the isoindole occurs on liberation of the primary amino group using hydrazine (equation 18) (64JA4152). 

Results of a kinetic study of the formation of phthalide by dehydrobromination of a-bromo-o-toluic acid are believed to provide support for an intimate ion-pair mechanism for the pyrolysis of some types of halo acids in the gas phase.51... 

BROMO-3-METHYLBENZOIC ACID (m-Toluic acid, 2-bromo-)... 

The present procedure is that described by the submitters.3 a-Phthalimido-o-toluic acid has also been prepared by the acidolysis of the corresponding ethyl ester, obtained from the reaction of ethyl a-bromo-o-toluate with potassium phthalimide.8... 

Kupchan et al. achieved the first total synthesis of aristolochic acid involving photocyclization of substituted 2-iodostilbenes [410], Piperonal (689) provided a suitable skeleton to build ring A of aristolochic acid. It was reduced to the piperonoyl alcohol (690) with lithium aluminium hydride. Bromination of 690 afforded 6-bromopiperonoyl bromide (691). It was then hydrogenated to the corresponding 2-bromo-4,5-methylenedioxytoluene by w-butyllithium carbonation method. The toluic acid (693) was converted to acid chloride by oxalyl chloride, and bromination of acid chloride and by radiation with a 200-W tungsten lamp followed by methanolysis afforded the ester 694, which on treatment with silver nitrate produced methyl ester (695). 

Bromo-3-iiitro-4-toluic acid 206 171 Nitrile, 130, subi... 

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