Benzoates reduction

Alkyl Benzoates. Reduction of benzaldehyde with four-fold excess of LiAlH4 may be dangerous.4... 

NOTE. Many esters reduce Fehling s solution on warming. This reduction occurs rapidly with the alkyl esters of many aliphatic acids, but scarcely at all with similar esters of aromatic acids (f.g., ethyl oxalate reduces, but ethyl benzoate does not). Note also that this is a property of the ester itself thus both methyl and ethyl oxalate reduce Fehling s solution very rapidly, whereas neither oxalic acid, nor sodium oxalate, nor a mixture of the alcohol and oxalic acid (or sodium oxalate), reduces the solution. 

Organotelluriumfll and IV) compounds undergo transmetallation with Pd(II)[414], The carbonylation of the alkenylphenyltellurium(II) 459 gives the a,/3-Unsaturated ester 460 and benzoate, 460 being the main product[415], Reductive coupling of diaryl, dialkyl, and aryl alkyltellurides 461 to give 462 proceeds by treatment with Pd(OAc)2[416,417],... 

Dehydrocholesterol has also been made from cholesterol by the Windaus procedure (Pig. 2) the 3,7-dibenzoate (16) is obtained (via (14) and (15) by oxidation and reduction), which undergoes thermal elimination to give the 7-dehydrocholesteryl benzoate (11) (42—44). However, the yields are substantially lower than those achieved by the brornination—dehydrobrornination method. 

As practiced by Hoffmann-La Roche, the commercial synthesis of vitamin is outlined ia Figure 1. Oxidation of 2-methylnaphthalene (4) yields menadione (3). Catalytic reduction to the naphthohydroquinone (5) is followed by reaction with a ben2oating reagent to yield the bis-benzoate (6). Selective deprotection yields the less hindered ben2oate (7). Condensation of isophytol (8) (see Vitamins, vitamins) with (7) under acid-cataly2ed conditions yields the coupled product (9). Saponification followed by an air oxidation yields vitamin (1) (29). 

A benzoate ester can be cleaved in 60-90% yield by electrolytic reduction at -2.3... 

An example of this reaction is the reaction of cyclohexene with t-butyl perbenzoate, which is mediated by Cu(I). " The initial step is the reductive cleavage of the perester. The t-butoxy radical then abstracts hydrogen from cyclohexene to give an allylic radical. The radical is oxidized by Cu(II) to the carbocation, which captures benzoate ion. The net effect is an allylic oxidation. 

Reduction of ethyl 3-[(2-fcrf-butoxycarbonylperhydropyrido[l,2-a]pyra-zin-7-yl)methoxy]benzoate with LAH in THF at room temperature yielded... 

Other corrosion inhibitors also enhance passivity without electrochemical reduction, by depositing insoluble oxidation products into the passivating film. For example benzoate ions cause deposition of ferric benzoate into the oxide, but do not provide any cathodic reaction. 

Some reactions of PtMe4L2 systems do not involve reductive elimination thus reaction of PtMe4(NN) (NN = phen, bipy) with organic acids yielding PtMe3A(NN) (A = formate, acetate, benzoate, salicylate) is first order in both reactants [201]. 

From a study of the decompositions of several rhodium(II) carboxylates, Kitchen and Bear [1111] conclude that in alkanoates (e.g. acetates) the a-carbon—H bond is weakest and that, on reaction, this proton is transferred to an oxygen atom of another carboxylate group. Reduction of the metal ion is followed by decomposition of the a-lactone to CO and an aldehyde which, in turn, can further reduce metal ions and also protonate two carboxyl groups. Thus reaction yields the metal and an acid as products. In aromatic carboxylates (e.g. benzoates), the bond between the carboxyl group and the aromatic ring is the weakest. The phenyl radical formed on rupture of this linkage is capable of proton abstraction from water so that no acid product is given and the solid product is an oxide. 

Benzoyl-CoA reductase carries out the two-electron reduction of the aromatic ring dnring the anaerobic degradation of benzoate by Thauera aromatica. This involves two-electron transfer from ferredoxin, and a combination of EPR and Mossbaner spectroscopy showed the presence of three different clusters, while inactivation by oxygen was associated with partial conversion of [4Fe-4S] clnsters to [3Fe-4S] clnsters (Boll et al. 2000). 

It has become clear that benzoate occupies a central position in the anaerobic degradation of both phenols and alkylated arenes such as toluene and xylenes, and that carboxylation, hydroxylation, and reductive dehydroxylation are important reactions for phenols that are discussed in Part 4 of this chapter. The simplest examples include alkylated benzenes, products from the carboxylation of napthalene and phenanthrene (Zhang and Young 1997), the decarboxylation of o-, m-, and p-phthalate under denitrifying conditions (Nozawa and Maruyama 1988), and the metabolism of phenols and anilines by carboxylation. Further illustrative examples include the following ... 

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