Benzoic acid carboxyl

Acrylic Acid Propenoic Acid Benzoic Acid Carboxylic Acids Carboxylic Acids and Derivatives Carboxylic Acids with Other Functional Groups Carboxylic Acids with Other Functional Groups Dichlorophenoxyacetic Acid 2,4-d Cesium... 

MURFITT, L. M., KOLOSOVA, N., MANN, C. J., DUDAREVA, N Purification and characterization of S-adenosyl-L-methionine Benzoic acid carboxyl methyltransferase, the enzyme responsible for biosynthesis of the volatile ester methyl benzoate in flowers of Antirrhinum majus., Arch Biochem. Biophys., 2000, 382,145-151. 

KOLOSOVA, N SHERMAN, D., KARLSON, D DUDAREVA, N., Cellular and subcellular localization of S-adenosyl-L- methionine Benzoic acid carboxyl... 

Quinoline Alkaloids.—Anthranilic acid and a benzoylacetic acid derivative, derived from phenylalanine, are precursors for graveoline (124) cf. ref. 5. On the other hand, whilst the biosynthesis of (125) no doubt involves anthranilic acid, benzoic acid (carboxyl-labelled material), and not phenylalanine, was a precursor for (125) in Lunasia amara incorporation was specific, with labelling of C-2. The remaining carbons should derive from acetate, and a positive incorporation was recorded. It is clear that further work is required on the biosynthesis of this alkaloid before its origins can be described with certainty. 

Eligh yields of esters are obtained from both acid-sensitive (cyanoacetic acid) and base-sensitive carboxylic acids (3-phenyl-propionic acid and trichloroacetic acid) and, in these latter cases, use of 4-(dimethylamino)pyridinium chlorosulfite chloride is much more effective than use of thionyl chloride alone. The esterification process has been claimed to be independent of the steric environment of the carboxyl function, though this reagent may be of more limited value with heavily substituted benzoic acids. Carboxyl activation, in the presence of a primary amine, leads to the corresponding amide in excellent yield (eq 2). In both the esterification and amidation processes and the oxime dehydration reaction discussed below, recovery of DMAP is straightforward. 

BAMT benzoic acid carboxyl methyl transferase... 

Reduction of the benzoic acid carboxyl groups yields the corresponding aldehydes and alcohols, as for instance vanilhn and vanillyl alcohol (XVII and XVIII respectively in Formula 18.18) from 3-methoxy-4-hydroxybenzoic acid and coniferyl alcohol from ferulic acid. 

A limitation of the ap and tt descriptors is the specificity of the atom typing, e.g., benzoic acid and phenyltetrazole would not be perceived as very similar, even though carboxylates and tetrazoles are both anions at physiological pH. 

When the phenol contains a carboxylic acid group, e.g., m- or p-hydroxy-benzoic acid, the acetylated derivative will of course remain in solution as the sodium salt, but is precipitated when the solution is subsequently acidified. Salicylic acid, however, cannot be acetylated under these conditions. 

Benzoic anhydride (carboxylic acid - acetic anhydride method). 

Aryl- or alkenylpalladium comple.xcs can be generated in situ by the trans-metallation of the aryl- or alkenylmercury compounds 386 or 389 with Pd(Il) (see Section 6). These species react with 1,3-cydohexadiene via the formation of the TT-allylpalladium intermediate 387, which is attacked intramolecularlv by the amide or carboxylate group, and the 1,2-difunctionalization takes place to give 388 and 390[322]. Similarly, the ort/trt-thallation of benzoic acid followed by transmetallation with Pd(II) forms the arylpalladium complex, which reacts with butadiene to afford the isocoumarin 391, achieving the 1,2-difunctionalization of butadiene[323]. 

Benzoic acid and naphthoic acid are formed by the oxidative carbonylation by use of Pd(OAc)2 in AcOH. t-Bu02H and allyl chloride are used as reoxidants. Addition of phenanthroline gives a favorable effect[360], Furan and thiophene are also carbonylated selectively at the 2-position[361,362]. fndole-3-carboxylic acid is prepared by the carboxylation of 1-acetylindole using Pd(OAc)2 and peroxodisulfate (Na2S208)[362aj. Benzoic acid derivatives are obtained by the reaction of benzene derivatives with sodium palladium mal-onate in refluxing AcOH[363]. 

It IS hard to find a class of compounds in which the common names of its members have influenced organic nomenclature more than carboxylic acids Not only are the common names of carboxylic acids themselves abundant and widely used but the names of many other compounds are derived from them Benzene took its name from benzoic acid and propane from propionic acid not the other way around The name butane comes from butyric acid present m rancid butter The common names of most aldehydes are derived from the common names of carboxylic acids—valeraldehyde from valeric acid for exam pie Many carboxylic acids are better known by common names than by their systematic ones and the framers of the lUPAC rules have taken a liberal view toward accepting these common names as permissible alternatives to the systematic ones Table 19 1 lists both common and systematic names for a number of important carboxylic acids... 

Carboxylic acids are fairly polar and simple ones such as acetic acid propanoic acid and benzoic acid have dipole moments m the range 1 7-1 9 D... 

A considerable body of data is available on the acidity of substituted benzoic acids Ben zoic acid Itself is a somewhat stronger acid than acetic acid Its carboxyl group is attached to an sp hybridized carbon and ionizes to a greater extent than one that is attached to an sp hybridized carbon Remember carbon becomes more electron withdrawing as its s character increases... 

Table 19 3 lists the ionization constants of some substituted benzoic acids The largest effects are observed when strongly electron withdrawing substituents are ortho to the carboxyl group An o nitro substituent for example increases the acidity of benzoic acid 100 fold Substituent effects are small at positions meta and para to the carboxyl group In those cases the values are clustered m the range 3 5-4 5... 

Because cyano groups may be hydrolyzed to carboxylic acids (Section 20 19) the Sand meyer preparation of aryl nitriles is a key step m the conversion of arylammes to sub stituted benzoic acids In the example just cited the o methylbenzomtnle that was formed was subsequently subiected to acid catalyzed hydrolysis and gave o methylbenzoic acid in 80-89% yield... 

As discussed earlier in Section lOC.l, ultraviolet, visible and infrared absorption bands result from the absorption of electromagnetic radiation by specific valence electrons or bonds. The energy at which the absorption occurs, as well as the intensity of the absorption, is determined by the chemical environment of the absorbing moiety. Eor example, benzene has several ultraviolet absorption bands due to 7t —> 71 transitions. The position and intensity of two of these bands, 203.5 nm (8 = 7400) and 254 nm (8 = 204), are very sensitive to substitution. Eor benzoic acid, in which a carboxylic acid group replaces one of the aromatic hydrogens, the... 

Synthetic phenol capacity in the United States was reported to be ca 1.6 x 10 t/yr in 1989 (206), almost completely based on the cumene process (see Cumene Phenol). Some synthetic phenol [108-95-2] is made from toluene by a process developed by The Dow Chemical Company (2,299—301). Toluene [108-88-3] is oxidized to benzoic acid in a conventional LPO process. Liquid-phase oxidative decarboxylation with a copper-containing catalyst gives phenol in high yield (2,299—304). The phenoHc hydroxyl group is located ortho to the position previously occupied by the carboxyl group of benzoic acid (2,299,301,305). This provides a means to produce meta-substituted phenols otherwise difficult to make (2,306). VPOs for the oxidative decarboxylation of benzoic acid have also been reported (2,307—309). Although the mechanism appears to be similar to the LPO scheme (309), the VPO reaction is reported not to work for toluic acids (310). 

Pyrrole Carboxylic Acids and Esters. The acids are considerably less stable than benzoic acid and often decarboxylate readily on heating. However, electron-withdrawing substituents tend to stabilize them toward decarboxylation. The pyrrole esters are important synthetically because they stabilize the ring and may also act as protecting groups. Thus, the esters can be utilized synthetically and then hydrolyzed to the acid, which can be decarboxylated by heating. Often P-esters are hydrolyzed more easily than the a-esters. 

In its chemical behavior benzoic acid shows few exceptional properties the reactions of the carboxyl group are normal, and ring substitutions take place as would be predicted. 

The hydroxyl group of the resulting phenol is situated immediately adjacent to where the carboxyl group was previously located. This same Hquid-phase copper oxidation process chemistry has been suggested for the production of cresols by the oxidation of toluic acids. y -Cresol would be formed by the oxidation of either ortho or para toluic acids a mixture of 0- and -cresols would be produced from y -toluic acid (6). A process involving the vapor-phase catalytic oxidation of benzoic acid to phenol has been proposed, but no plants have ever been built utilizing this technology (27). 

It will be noted that pyrrole-3-carboxylic acid (154) is an appreciably weaker acid than benzoic acid and this is attributed to the stabilization of the undissociated acid by electron release from nitrogen. The 2-carboxylic acids of furan, thiophene, selenophene and tel-lurophene are all stronger acids than benzoic acid, tellurophene-2-carboxylic acid (pisTa 4.0) being the weakest acid in this series (77AHC(21)119). 

The present method for preparing aromatic dicarboxylic acids has been used to convert phthalic or isophthalic acid to tereph-thalic acid (90-95%) 2,2 -biphenyldicarboxylic acid to 4,4 -biphenyldicarboxylic acid 3,4-pyrroledicarboxylic acid to 2,5-pyr-roledicarboxylic acid and 2,3-pyridinedicarboxylic acid to 2,5-pyridinedicarboxylic acid. A closely related method for preparing aromatic dicarboxylic acids is the thermal disproportionation of the potassium salt of an aromatic monocarboxylic acid to an equimolar mixture of the corresponding aromatic hydrocarbon and the dipotassium salt of an aromatic dicarboxylic acid. The disproportionation method has been used to convert benzoic acid to terephthalic acid (90-95%) pyridine-carboxylic acids to 2,5-pyridinedicarboxylic acid (30-50%) 2-furoic acid to 2,5-furandicarboxylic acid 2-thiophenecar-boxylic acid to 2,5-thiophenedicarboxylic acid and 2-quinoline-carboxylic acid to 2,4-quinolinedicarboxylic acid. One or the other of these two methods is often the best way to make otherwise inaccessible aromatic dicarboxylic acids. The two methods were recently reviewed. ... 

Detection and result The chromatogram was freed from mobile phase and immersed for 3 s in the dipping solution and heated to 125°C for 5 — 10 min. The carboxylic acids terephthalic acid (tiRi 5), succinic acid (fiRi 50 — 55), phthalic acid (hRf 55 — 60), suberic acid (tiRi 60 — 65), sebacic acid (fiRi 65 — 70), benzoic acid (tiRi 75 — 80) and salicylic acid (hRf 80 — 85) yielded brown zones on a light brown background. The detection limit was 2 pg acid per chromatogram zone. 

Fig. 1 Schematic representation of the chromatographic separation of carboxylic acids. Maleic acid (1), pimelic acid (2), succinic acid (3), benzoic acid (4), malic acid (5), tartaric acid (6), lactic acid (7), stearic acid (8), arachidic acid (9), suberic acid (10), mixture (M).

Oxidation by Chromic Acid. Under mild conditions, e.g., in acetic acid at atmospheric temperature this converts the dihydric alcohol or keto-alcohol bases to diketo-bases, e.g., the lelobanidines, Ci3H2902N, to lelobanines, C13H25O2N. Under more vigorous action the keto-alcohol and the diketo-bases are oxidised to benzoic acid (side-chain, Ph. CO. ), acetic and i iropionic acids (side-chain, C2H5. CO. ) and either scopolinic acid l-methylpiperidine-2 6-dicarboxylic acid (IV)) or methylgranatic acid (l-methylpiperidine-2-carboxylic-6-acetic acid) or both, these being from the methylpiperidine nucleus with residues of the two side-chains. 

The reduction is general for a variety of substituted benzophenones Such substituents as CH3 OH, OCH3, F, Br. N(CH3)2, NO2. COOH, COOCH3, NHCOC Hreaction conditions and do not alter the course of the reduction Diarylmethanols are reduced to diarylmethanes under the same conditions and probably are the intermediates in the reduction of ketones [26] Triethylsilane also can be used as a reducing agent in trifluoroacetic acid medium [27J This reagent is used for the reduction of benzoic acid and some other carboxylic acids under mild condiUons (equation 14) Some acids (phthalic, sue cinic, and 4-nitrobenzoic) are not reduced under these conditions [27]... 

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