Toluic acid derivs

Preparation of iron-encapsuled pyridiyl-substituted porphyrin toluic acid derivative... 

The mechanism of oxidation of / -toluic acid with MC catalyst has not been studied in great detail since the early paper by Ravens (which was one of the first papers on MC cobalt-bromide oxidation) [66]. We assume that the mechanism of oxidation of the second methyl group is the same as the first one, but the reaction rate constants may be very different for /j-toluic acid-derived radicals and hydroperoxides [33]. This is an area that deserves further investigation. 

An additional useful test is to distil the acid or its sodium salt with soda lime. Heat 0.5 g. of the acid or its sodium salt with 0 2 g. of soda lime in an ignition tube to make certain that there is no explosion. Then grind together 0-5 g. of the acid with 3 g. of soda hme, place the mixture in a Pyrex test-tube and cover it with an equal bulk of soda hme. Fit a wide dehvery tube dipping into an empty test-tube. Clamp the tube near the mouth. Heat the soda lime first and then the mixture gradually to a dull-red heat. Examine the product this may consist of aromatic hydrocarbons or derivatives, e.g., phenol from sahcyUc acid, anisole from anisic acid, toluene from toluic acid, etc. 

For initial experience in the uae of Uthium, the preparation of either p-toluic acid or of a-napbtboic acid mcay be undertaken. For the former, p-bromotoluene is converted into the lithium derivative and the latter carbonated with soUd carbon dioxide ... 

Terephthalic acid has been obtained from a great many /)-disubstituted derivatives of benzene or cyclohexane by oxidation with permanganate, chromic acid, or nitric acid. The following routes appear to have preparative value from />-toluic acid, />-methylacetophenone,2 or dihydro-/)-tolualdehyde by oxidation with permanganate from f>-cymene by oxidation with sodium dichromate and sulfuric acid from />-dibromobenzene or from /i-chloro- or -bromobenzoic acid by heating at 250° with potassium and cuprous cyanides and from />-dibromo-benzene, butyllithium, and carbon dioxide. ... 

Hercules Chemical produced an acidic organic waste derived from the manufacture of dimethyl terphthalate, which is used in the production of synthetic liber. The average dissolved organic carbon concentration was about 7100 mg/L and included acetic acid, formic acid, p-toluic acid, formaldehyde, methanol, terphthalic acid, and benzoic acid. The pH ranged from 3.5 to 4.0. The waste also contained traces (less than 0.5 mg/L) of 11 other organic compounds, including dimethyl phthalate, a listed hazardous waste. 

The chiral auxiliaries anchored to the substrate, which is subjected to diastereoselective catalysis, is another factor that can control these reactions. These chiral auxiliaries should be easily removed after reduction without damaging the hydrogenated substrate. A representative example in this sense is given by Gallezot and coworkers [268], They used (-)mentoxyacetic acid and various (S)-proline derivates as chiral auxiliaries for the reduction of o-cresol and o-toluic acid on Rh/C. A successful use of proline derivates in asymmetric catalysis has also been reported by Harada and coworkers [269,270], The nature of the solvent only has a slight influence on the d.e. [271],... 

An improved procedure for the synthesis of (478) has been reported recently [185, 207, 209]. An attractive feature of this approach is that it provides entry to related pharmacologically interesting 10-alkyl-10-deazaAP derivatives (,Scheme 3.96). Treatment ofp-toluic acid (481a) with two equivalents of LDA,... 

Similar flash vacuum pyrolysis of o-toluic acid chloride (561) lends itself to the easy preparation of benzocyclobutenone (563) (76% at a laboratory scale of 250 g). Variations of the aromatic nucleus are easy, as demonstrated by the preparation of derivatives (564)- 567) (Scheme 130). 

This acid is the simplest aromatic acid with the carboxyl in the side chain. Its name, phenyl acetic acid, indicates the relation to the aliphatic acids as a phenyl derivative. The commonly used names for the side-chain carboxy acids are derived similarly, e.g. phenyl propiolic acid. It will be seen at once that phenyl acetic acid and the toluic acids are isomeric, the first being the result of the partial oxidation of ethyl benzene, the latter the result of the partial oxidation of the di-methyl benzenes or xylenes which are isomeric with ethyl benzene. In both cases the relationship to the hydrocarbon is that only one carbon group of the side chain is oxidized to carboxyl. 

Derivatives of Menthene.— The most important alcohols and ketones derived from the menthene unsaturated group of terpenes are terpineol, di-hydro carveol, di-hydro carvone and pulegone. The first one, the alcohol terpineol, occurs in its dextro form in cardamon oil and marjoram oil, in its leoo form in neroU oil and in its inactive form in cajeput oil. The constitution is proven by Perkin s synthesis from As-tetra-hydro para-toluic acid by means of the Grignard reaction. 

Derivation (o-) Benzene and o-toluic acid chloride (aluminum chloride catalyst) (p-) benzoyl peroxide + toluene (aluminum chloride catalyst). 

Derivation Catalytic oxidation of o-toluic acid and oxidation of xylene. 

Mel nikov, N.N., Mandel baum, Y.A., and Lomakina, V.L, Organic insectofungicides. Part 58. Synthesis of some derivatives of dialkoxyphosphonopropionic, butyric, and toluic acids, Zh. Obshch. Khim., 31, 849, 1961 J. Gen. Chem. USSR (Engl. Transl.), 31, 781, 1961. 

The methyl ester 1 was prepared by coupling (5)-proline with o-toluic acid, via the corresponding acyl chloride, and derivation of the acid obtained to the methyl ester, as described in the previous report [7]. 

In many cases the aromatic carboxylic acids are named, in either system, as derivatives of benzoic acid. Generally, the -oic acid or -ic acid suffix is attached to the appropriate prefix. However, "common names" of substituted benzoic acids (for example, toluic acid and phthalic acid) are frequently used. 

Because the original synthesis of 10-deazaAMT (IV.91) via the Boon-Leigh approach had given an overall yield of only 5%, DeGraw et al. [123] subsequently developed also a modified Waller-type scheme that not only proceeded in somewhat better overall yield but was amenable to the preparation of 10-alkyl-10-deaza derivatives. Condensation of 3-methoxyallyl chloride in situ with the dianion of p-toluic acid (generated with 2 equivalents of lithium diisopropylamide in cold THE) yielded the enol ether (IV. 102). On bromi-nation and mild acid hydrolysis at pH 1-2, (IV. 102) gave the a-bromoalde-... 

An excess of alkali may be added at the start, in which condition potassium permanganate is used for oxidizing ortho-substituted derivatives of toluene. Thus, o-toluic acid yields phthalic acid. Substituted cinnamic acids are oxidized to the corresponding benzoic acids. Triphenylmethane is oxidized to the corresponding alcohol, diphenylmethane4,o the ketone, and oleic acid to dihydroxystearic acid. 

Dihydroisocoumarins are conveniently obtained from the reaction of aldehydes and ketones with the dianions derived from o-toluic acids, though the products are not always stereochemically pure (94SC779). However, enantiomerically pure dihydroisocoumarins result from the stereoselective reduction of (arene)-tricarbonylchromium cmnplexes of homobenzylic ketones by DIB ALH, followed by oxidation of the resulting lactols (94CCS01). 

Nitro-toluic acid—Nitro-terephthalic acid — Nitro-iso-phthalic acjd—aiai-Nitro-naphthalene>sulphonic acid...63-65 Reaction of Gattermann — Nitro-toluenes—Nitro-p-xylene— Ldb s experiments — Aromatic nitramines — Nitro-car-boxylic acids—Nitro-sulphonic acids—Nitro-derivatives... 

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