And oxidation of aromatic compounds

F. Effenberger, Acc. Chem. Res. 22,27-35 (1989) l,3,5-Tris(dialkylamino) benzenes Model Compounds for the Electrophilic Substitution and Oxidation of Aromatic Compounds". 

Degradative oxidation of aromatic rings into carboxylic acids4b and oxidation of aromatic compounds to quinones2a... 

The most important applications of peroxyacetic acid are the epoxi-dation [250, 251, 252, 254, 257, 258] and anti hydroxylation of double bonds [241, 252, the Dakin reaction of aldehydes [259, the Baeyer-Villiger reaction of ketones [148, 254, 258, 260, 261, 262] the oxidation of primary amines to nitroso [iJi] or nitrocompounds [253], of tertiary amines to amine oxides [i58, 263], of sulfides to sulfoxides and sulfones [264, 265], and of iodo compounds to iodoso or iodoxy compounds [266, 267] the degradation of alkynes [268] and diketones [269, 270, 271] to carboxylic acids and the oxidative opening of aromatic rings to aromatic dicarboxylic acids [256, 272, 271, 272,273, 274]. Occasionally, peroxyacetic acid is used for the dehydrogenation [275] and oxidation of aromatic compounds to quinones [249], of alcohols to ketones [276], of aldehyde acetals to carboxylic acids [277], and of lactams to imides [225,255]. The last two reactions are carried out in the presence of manganese salts. The oxidation of alcohols to ketones is catalyzed by chromium trioxide, and the role of peroxyacetic acid is to reoxidize the trivalent chromium [276]. 

Sanabria-Chinchilla J, Baricuatro JH, Soriaga MP, Hernandez F, Baltruschat H (2007) Electrocatalytic hydrogenation and oxidation of aromatic compounds studied by DBMS benzene and p-dihydroxybenzene at ultrathin Pd films electrodeposited (m Au(hkl) surfaces. J Colloid Interface Sci 314 152-159... 

CoF is used for the replacement of hydrogen with fluorine in halocarbons (5) for fluorination of xylylalkanes, used in vapor-phase soldering fluxes (6) formation of dibutyl decalins (7) fluorination of alkynes (8) synthesis of unsaturated or partially fluorinated compounds (9—11) and conversion of aromatic compounds to perfluorocycHc compounds (see Fluorine compounds, organic). CoF rarely causes polymerization of hydrocarbons. CoF is also used for the conversion of metal oxides to higher valency metal fluorides, eg, in the assay of uranium ore (12). It is also used in the manufacture of nitrogen fluoride, NF, from ammonia (13). 

Azo Coupling. The coupling reaction between an aromatic diazo compound and a coupling component is the single most important synthetic route to azo dyes. Of the total dyes manufactured, about 60% are produced by this reaction. Other methods iaclude oxidative coupling, reaction of aryUiydraziae with quiaones, and oxidation of aromatic amines. These methods, however, have limited iadustrial appHcations. 

Attenlion should be drawn to ihe use of tin oxide systems as heterogeneous catalysts. The oldest and mosi extensively patented systems are the mixed lin-vanadium oxide catalysis for the oxidation of aromatic compounds such as benzene, toluene, xylenes and naphthalene in the. synthesis of organic acids and acid anhydride.s. More recenily mixed lin-aniimony oxides have been applied lo the selective oxidaiion and ammoxidaiion of propylene to acrolein, acrylic acid and acrylonilrile. 

Oxepin and its derivatives have attracted attention for several reasons. Oxepin is closely related to cycloheptatriene and its aza analog azepine and it is a potential antiaromatic system with 871-elcctrons. Oxepin can undergo valence isomerization to benzene oxide, and the isomeric benzene oxide is the first step in the metabolic oxidation of aromatic compounds by the enzyme monooxygenase. 

Daly JW, DM Jerina, B Witkop (1972) Arene oxides and the NIH shift the metabolism, toxicity and carcinogenicity of aromatic compounds. Experientia 28 1129-1149. 

Reactions of partial electrochemical oxidation are of considerable interest in the electrosynthesis of various organic compounds. Thus, at gold electrodes in acidic solutions, olefins can be oxidized to aldehydes, acids, oxides, and other compounds. A good deal of work was invested in the oxidation of aromatic compounds (benzene, anthracene, etc.) to the corresponding quinones. To this end, various mediating redox systems (e.g., the Ce /Ce system) are employed (see Section 13.6). 

Intermediates generated at an electrode surface may react while still near the electrode. If so, one side of the intermediate may be wholly or partly shielded from attack by other reactants by the electrode itself. Such behavior is particularly common in the electrochemical oxidation of aromatic compounds since, as we have already seen with coumarin, aromatic compounds are generally tightly adsorbed parallel to the electrode surface at potentials positive of the p.z.c. For example, electrochemical oxidation of the stilbenes in alkaline methanol affords a mixture of dl and meso-1,2 dimethoxy-1,2-diphenylethane (1) 10>. It is found that c/s-stilbene affords a mixture of isomers of 1 in which the... 

Palmisano, G., Addamo, M., Augugliaro, V., Caronna, T., Garci a-Lopez, E., Loddo, V., and Palmisano, L. (2006) Influence of the substituent on selective photocatalytic oxidation of aromatic compounds in aqueous Ti02 suspensions. Chemical Communications (9), 1012-1014. 

Vazquez-Duhalt, R. Westlake, D. W. S., and Fedorak, P. M., Lignin Peroxidase Oxidation of Aromatic-Compounds in Systems Containing Organic-Solvents. Applied and Environmental Microbiology, 1994. 60(2) pp. 459-466. 

A broad spectrum of chemical reactions can be catalyzed by enzymes Hydrolysis, esterification, isomerization, addition and elimination, alkylation and dealkylation, halogenation and dehalogenation, and oxidation and reduction. The last reactions are catalyzed by redox enzymes, which are classified as oxidoreductases and divided into four categories according to the oxidant they utilize and the reactions they catalyze 1) dehydrogenases (reductases), 2) oxidases, 3) oxygenases (mono- and dioxygenases), and 4) peroxidases. The latter enzymes have received extensive attention in the last years as bio catalysts for synthetic applications. Peroxidases catalyze the oxidation of aromatic compounds, oxidation of heteroatom compounds, epoxidation, and the enantio-selective reduction of racemic hydroperoxides. In this article, a short overview... 

More drastic conditions of temperature, pressure and time gave carbon as the product from both aromatic and aliphatic compounds. This carbon is an activated char with decolorizing properties. Tars, tarry substances, the oxides of carbon, and the usual products of the oxidation of aromatic compounds (dicarboxylic acids) were all conspicuous by their absence. Benzotrifluoride oxidized to benzoyl fluoride. The aliphatic compounds cyclohexane, methycyclohexane, n-heptane, etc., could be oxidized to carbon and water. 

Besides a variety of other methods, phenols can be prepared by metal-catalyzed oxidation of aromatic compounds with hydrogen peroxide. Often, however, the selectivity of this reaction is rather poor since phenol is more reactive toward oxidation than benzene itself, and substantial overoxidation occurs. In 1990/91 Kumar and coworkers reported on the hydroxylation of some aromatic compounds using titanium silicate TS-2 as catalyst and hydrogen peroxide as oxygen donor (equation 72) . Conversions ranged from 54% to 81% with substituted aromatic compounds being mainly transformed into the ortho-and para-products. With benzene as substrate, phenol as the monohydroxylated product... 

Some reactions of 2,2 -bipyridine /V-oxides have been reported. The l,T-dioxide is nitrated readily to 4,4 -dinitro-2,2 -bipyridine 1,T-dioxide. ° ° °" 2,2 -Bipyridine 1-oxide is also nitrated in the 4 position. The nitro groups in 4,4 -dinitro-2,2 -bipyridine l,T-dioxide are reactive, being replaced by chlorine with concentrated hydrochloric acid," by bromine with acetyl bromide, by hydroxyl with dilute sulfuric acid, and by alkoxy groups with sodium alkoxides. Some of the dialkoxy derivatives are useful catalysts for the oxidation of aromatic compounds. The dinitro dioxide is deoxygenated to 4,4 -dinitro-2,2 -bipyridine with phosphorus trichloride in chloroform, and other substituted l,T-dioxides behave similarly, but with phosphorus trichloride alone, 4,4 -dichloro-2,2 -bipyridine results. The dinitro dioxide is reduced by iron powder in acetic acid to 4,4 -diamino-2,2 -bipyridine, whereas 4,4 -dichloro-2,2 -bipyridine l,T-dioxide is converted to its 4,4 -diamino analogs with amines. Related reactions have been described. ... 

A principally different approach for the indirect electrochemical oxidation of aromatic compounds goes via the formation of hydroxyl radicals from cathodically generated hydrogen peroxide and from reductively formed iron(II) ions. The thus in situ formed Fenton reagent can lead to side-chain as well as nuclear oxidations of aromatic compounds. Side-chain oxidations to form benzaldehydes according to Eqs. (18)—(24) can also be initiated by the redox pairs and Cu instead of... 

Formation of Aromatic Compounds A scientific challenge comparable to that of developing oxidation mechanisms for the large hydrocarbon fuels is understanding and describing quantitatively the formation and oxidation of aromatic and polycyclic aromatic compounds (PAH) formed in combustion processes. Aromatic compounds are known to be harmful to the environment, and the emission of these species from a number of combustion systems is a significant concern. Furthermore aromatic species are important pre-... 

In addition to being oxidized by the hydroxyl radical, alkenes may react with the N03 radical as has been described by several investigators (52, 56, 66). Listed in Table I are some of the organic nitrates that have been predicted to be produced via reaction of OH and N03 with isoprene and pro-pene. Analogous compounds would be expected from other simple alkenes and from terpenes such as a- and (3-pinene. Other possible organic nitrates may be produced via the oxidation of aromatic compounds (53, 54) and the oxidation of carbonaceous aerosols (67). Quantitative determination of these species has not been made in the ambient atmosphere. 

Calvert and McQuigg suggest that yet unknown radicals, such as 0CH20 or those derived from it, formed in the 03-olefin-air mixtures may oxidize S02 in the homogeneous reaction. It is known that OH and H02 radicals combine rapidly with S02. The addition products may eventually be transformed into sulfuric acid, peroxysulfuric acid, sulfates, and nitrates in a polluted atmosphere probably in a liquid phase of aerosol particles, although the detailed steps are still unknown. Finlayson and Pitts (357) believe that the oxidation of aromatic compounds by such species as OH, H02, 03, and 0(3P) may also be significant for the formation of organic aerosol. 

WOLFFENSTEIN-BOTERS REACTION. Simultaneous oxidation and nitration of aromatic compounds to nitrophcnols with nitric acid or the higher oxides of nitrogen in the presence of a mercury salt as catalyst. Hydroxynitration of benzene yields picric acid. 

Mokrini, A., Ousse, D., and Espuglas, S., Oxidation of aromatic compounds with UV radiation/ozone/hydrogen peroxide, Water Sci. Technol., 35, 95-102, 1997. 

Deoxygenation of pyridine A-oxides has been achieved using dimethyldioxiran <95CC1831> and palladium with sodium hypophosphite <95GCI(124)385>. Pyridine A-oxides, with ruthenium porphyrin catalysts, have been used as an oxidant of aromatic compounds <95JA(117)8879> or olefins, alcohols, sulfides and alkanes <95FI(40)867>. 

Choudhary, V. R., Jana, S. K., Patil, N. S., Bhargava, S.K. Friedel-Crafts type benzylation and benzoylation of aromatic compounds over I l/i zeolite modified by oxides or chlorides of gallium and indium. Microporous Mesoporous Mater., 2003, 57, 21-35. 

Two-electron redox phenomena are rare for Cu, and therefore Cu is not a suitable catalyst for epoxidations, for example. However, Cu is useful for free radical reactions such as deep oxidation of organic molecules in waste streams and ring or side chain oxidation of aromatic compounds. 

Fenton reagent generated in situ — Indirect electrochemical oxidation of aromatic compounds (e.g., benzene to phenol) proceeds with the Fenton reagent generated in situ electrochemically at the cathode by the reduction of ferric to ferrous salt and by the reduction of oxygen to hydrogen peroxide... 

Fig. 7 Illustration of cyclic voltammograms for consecutive oxidations of aromatic compounds to cation radicals and dications. (Hammerich and Parker, 1973)...

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