2- benzoic add derivative

Louhichi, B., Bensalash, N. and Gadri, A. (2006), Electrochemical oxidation of benzoic add derivatives on boron doped diamond Voltammetric study and galvanostatic electrolyses. Chem. Eng. Technol., 29(8) 944-950. 

I) gives benzyl alcohol, a well-known fragrance (2) gives benzaldehyde and (3) benzoic add derivatives... 

Fig. 3.4 Some common simple plant phenolic adds, cinnamic acid derivatives on the right and benzoic add derivatives on the left, where H equals hydrogen, OH equals hydroxy, and OMe equtils methoxy...

From the results of Malek et al.49,561 m 205,206,211) it may be concluded that the various metal derivatives used in esterifications exhibit many common catalytic characteristics. Thus, these authors190 established relationships concerning the free energies of esterification of thirteen ortho-, meta- and para-substituted benzoic adds by 1,2-ethanediol. They obtained Hammett parameters which do not differ greatly from those found for the add-catalyzed esterifications of the same adds with various alcohols. They concluded... 

Chand P, Kotian PL, Morris PE, Bantia S, Walsh DA, Babu YS (2005b) Synthesis and inhibitory activity of benzoic add and pyridine derivatives on influenza neuraminidase. Bioorg Med Chem 13 2665-2678... 

Sandmeyer s synthesis of aromatic nitriles is far more elegant than the removal of water from the ammonium salts of carboxylic acids, which latter reaction is also applicable to benzene derivatives. In particular, the former synthesis permits of the preparation of carboxylic acids via the nitriles, and so provides a complete substitute for Kolbe s synthesis (alkyl halide and potassium cyanide), which is inapplicable to aromatic compounds. The simplest example is the conversion of aniline into benzoic add. The converse transformation is Hofmann s degradation (benzamide aniline, see p. 152). 

Amino-3-fluorobenzoic acid is an important intermediate in the synthesis of derivatives of indole, such as the potent and selective thromboxane/prostaglandin endoperoxide receptor antagonist L-670,596 or the anti-inflammatory agent Etodolac. Compounds of this type have therapeutic applications. 2-Amino-3-fluoro-benzoic add is aiso an important precursor for the synthesis of fluoroacridines, which can be converted to interesting tridentate ligands, such as Acriphos. ... 

In a similar manner Crabb and Schofield852 have described 11n lactonisathm effect in the per benzoic add epaxidation of certain substituted benzocycloheptone derivatives, and Howell and Taylor - did so for the reaction of an indeno, ae shown in Eq . (46) and (47). 

Berti and Bottari l s 149 reported that epoxidation of o-carboxy-tmns-Htilbcnc with per benzoic add is a Btoreospccific reaction that can yield either of two lactones (XLII) and (XLITT), depending ou the temperature (Eq. 42). Two lactones (XLlV) and (XLV) can likewise be formed from the corresponding ets-stilbene derivative, the predominance of one over the other being again temperature-dependant (Eq. 43). The five-membered lactones (XLII) and (XLIV) appear (i> be favored at low temperatures. 

This gradation is illustrated by the results obtained with the diazonium salts from the isomeric aminobenzoic adds. When the orthQ diazonium nitrate is treated with absolute ethanol only reduction occurs 23 ethyl benzoate is obtained in 63% yield.f The diazonium add sulfate derived from ra-aminobenzoic add is converted into a mixture of ethyl benzoate and ethyl m-ethoxybenzoate, the former preponderating.24 23122 Finally, with the p-diazonium salts the ether reaction is the favored one 22123 from the nitrate the yields of p-ethoxy benzoic add and ethyl benzoate are 60% and 12%, respectively. 

When 4-hydroxy benzoic acid was used in place of phenol, most of the 4-hydro-xybenzoic add derivatives crystallised out on addition of the crude reaction mixture to water, the remainder being removed by base extraction of the filtrate. 

Photoreactions involving benzoic add are not common, but it is now reported that the arene moiety is susceptible to substitution in the presence of sodium hypochlorite in aqueous alkali at pH > 12. At ratios of the order of 0.1 for [Q0 ] [PhC02 l, hydroxylation and chlorination of the aromatic ring occur simultaneously with ipso substitution at the carboxylate group (which yields phenol). At high relative concentrations of hypochlorite, the photo-products react further in the dark to yield polychlorinated derivatives. The reaction is discussed in terms of the initial steps being the generation of the active species 0( P), 0( D), O, and Cl from irradiation of C10 . 

When a benzoic acid derivative is reduced, the final protonation step does not occur, and a carboxylate enolate is obtained. The enolate can be protonated upon workup to give the usual product, or it can be alkylated by addition of an electrophile. The proton or the electrophile adds ipso to the carboxylate group exclusively. This position has the largest coefficient in the HOMO of the pentadienyl anion. 

N and Z are complex stereoisomeric intermediates explicitly definedin Scheme XVI of 39). Y is a mixture of the (S, S)- and (R, R)-valine derivatives. The starting materials are isobutyraldehyde-(S)-a-phenylethylimine (A) benzoic add (B), and t-butylisocyanide (C). X5 is the benzoate ion, CeHaCOO . It should be noted that none of the rate steps occur until t-butyl isocyanide (C) is added and that, at a constant temperature, spedal conditions are obtained by varpng the initial concentration of A, B, C, H+ or X5. Parameters are equilibrium constants, rate constants, and concentration-time data for all the chemical compounds or intermediates that are involved. 

The squalestatins, e.g. 6.28, also known as the zaragozic adds, have attracted considerable interest as inhibitors of squalene synthase and hence of cholesterol biosynthesis and lipid deposition in the circulatory system. They are also inhibitors of farnesyl protein transferase and thus they may have other potentially useful biological applications. They are formed by Phoma spedes and also by Setosphaeria khartoumensis. The squalestatins are characterized by a dioxabicyclo-octane core bearing three carboxyl groups and two polyketide chains, one of which is attached as an ester. The biosynthetic incorporation of succinic acid into part of the bicyclo-octane, together with its oxygenation pattern, indicate that it may be derived via oxaloacetic acid. Both the polyketide chains have several pendant methyl groups attached to them, which arise from methionine, whilst benzoic add ads as a starter unit for one of the chains. These complex structures are thus the summation of several biosynthetic pathways. 

Forbes and co-workers9 have extensively studied the ultra-violet absorption spectra of several series of disubstituted benzene derivatives acetophenones, benzoic adds, benzaldehydes, phenylbenzoates, acetanilides- nitrobenzenes, anilines, fluorobenzenes, chlorobenzenes, phenols and anisoles. They have collected valuable data and interpreted them in terms of the resonance and steric interactions of substituents. Baliab. and co-workers27 have studied the absorption spectra of aryl sulphones and sulphoxides. The absorption spectra of substituted phenylazides28 and phenyl isothiocyanates29 have been discussed by Rao et al. 

Emantioseieetive Birch redmction-atkylation. lire chiral benzoic acid deriv ativc 1. prepared hy ccuidcnsatioit irf o-bydroxybenzcM add with L olinol fob lowed by cycltzation (Mitsunobu reaction), undergoes Birch reduction (K. NHt. HfF, r-butyl aloohot) (oltow cd by alkylation with essentially only 2. 

Imidazole, benzimidazole, and benzotriazole give N-phenyl derivatives in low yield with benzyne ° l-methylbenzotriazole understandably fails to react. In contrast, 2-methylbenzotriazole reacts with benzyne (from oxidation of 9 with lead tetraacetate) to give 1-phenylbenzotriazole (112) (22%). The mechanism suggested to account for incorporation of benzyne and oxidative removal of the JV-methyl group is outlined in Scheme 13 formaldehyde may be further oxidized under these conditions. 2-Benzylbenzotriazole and benzyne under the same conditions afforded 112 and benzoic add. When benzyne was generated from 4 instead, it reacted with 2-methylbenzotriazole to give phenazine (2%) and no 112. ... 

The structural and electronic analogies between the nitro and the imide groups have also been surveyed in this transformation (Scheme 4.69). Takemoto s catalyst has been employed in the reaction of thiophenol to imides derived from benzoic add, furnishing excellent yields of the sulfa-Michael... 

The 9,10-anthraquinone system is a classic example of an EE mechanism, which includes a synproportionation process. Absorbance versus distance profiles were measured for this reaction and the homogeneous and heterogeneous rate constants were in agreement with those derived from cychc voltammetry [169]. Protonation of the benzophenone anion radical by benzoic add and o-cresol was studied using this technique [170]. A variety of electrode geometries were explored in determining the heterogeneous... 

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