Aromatic hydrocarbons maleic anhydride with

Reaction of Maleic Anhydride with Aromatic Hydrocarbons under the Influence of Silent Electric Discharge at Atmospheric Pressure... 

A number of perylene derivatives undergo cyclo addition reaction. Hern-don has shown that the free energies of activation of the reaction of MA with aromatic hydrocarbon has a linear relationship with calculated resonance energy differences. This approach has significant prediction value (see Table 4.5). Recently, kinetic studies of the DA reaction of maleic anhydride with polycyclic aromatics have been reported. 

Acylation. In chlorinated solvents, maleic anhydride reacts with aromatic hydrocarbons (ArH) in the presence of aluminum chloride... 

Additions to Aromatic Hydrocarbons. A variety of photochemical additions to aromatic hydrocarbons have been reported. Benzene and its derivatives add to maleic anhydride74-76 as well as to simple olefins,77-80 isoprene,81 acetylene derivatives,79,82 and alcohols.83 The mechanism of the maleic anhydride-benzene reaction is discussed in Section IV. A.4. Naphthalene forms a photoadduct with dimethyl acetylenedicarboxylate62 and with acrylonitrile8211 while anthracene behaves similarly with maleic anhydride84 and with 1,2-benzanthracene.85 The photoaddition of several aromatic amines to anthracene has been reported to proceed via a charge transfer complex86,87 in fact, the majority of these addition reactions may proceed in this manner. 

Aromatic hydrocarbons which have methyl side chains mainly behave like toluene and form aldehydes, while combustion is stimulated and selective oxidation of the nucleus is repressed. The oxidation of methyl-naphthalene, for example, exhibits a low selectivity with respect to phtha-lic anhydride formation, combustion and maleic acid formation being the dominating reactions. Durene is a special case because it resembles o-xy-lene. The oxidation of durene over a V—W—O catalyst at 420° C is reported to produce pyromellitic dianhydride, phthalic and maleic anhydride, although combustion dominates (Geiman et al. [122]). 1,2,4-Trimethyl-benzene yields dimethylbenzene and trimellitic acid if oxidized on a Sn— V—O catalyst. Kinetic data have been measured by Balsubramanian and Viswanath [37]. 

The Diels-Alder reaction of benzenoid aromatic hydrocarbons with dienophiles was discovered more than fifty years ago [61, 62]. A classical example is the reaction of anthracene with maleic anhydride (Scheme 5). Although this type of reaction, termed endogenic or endocyclie Diels-Alder reaction, could be expected to be particularly well suited for correlating structure (topology) of benzenoid hydrocarbons with kinetic data, the problem has been systematically studied only very recently. Biermann and Schmidt in a series of publications [12, 29, 45, 63, 64] reported second-order rate constants (k2), measured under standard conditions (1,2,4-trichlorobenzene, 91.5 + 0.2 °C), for the endocyclie Diels-Alder reaction between maleic anhydride and 102 benzenoid hydrocarbons. Each rate constant was measured twice, the values usually... 

Experimental log k2 values were correlated with Brown para-localization energies, Dewar reactivity numbers, Herndon structure count ratios, Hess-Schaad resonance energy differences, indices of free valence, and second-order perturbation stabilization energies. The latter are based on Fukui s frontier orbital theory [67] which classifies the Diels-Alder reaction of benzenoid hydrocarbons with maleic anhydride as mainly HOMO (aromatic hydrocarbon)-LUMO (maleic anhydride) controlled. However, the corresponding orbital interaction energy given by... 

Benzenoid hydrocarbons, which like perylene (10) contain a peripheral cisoid C4 arrangement (a bay region [71]), react with maleic anhydride in the presence of a suitable dehydrogenating agent to form fully aromatic dicarboxylic acid anhydrides 12 ( benzogenic Diels-Alder reaction ) [72, 73], Since in this process the ratedetermining step is the exocyclic Diels-Alder reaction leading to 11, the reactivity behaviour of the system is dominated by the Jt-electronic properties of the hydrocarbon centres at which this primary reaction occurs [74]. 

Functionalization of hydrocarbons from petroleum sources is mainly concerned with the introduction of oxygen into the hydrocarbon molecule. In general, two ways are open to achieve oxygen functionalization oxidation and carbonylation. Oxidation is commonly encountered in the synthesis of aromatic acids, acrolein, maleic anhydride, ethene oxide, propene oxide, and acetaldehyde. Hydroformylation (CO/H2) (older literature and the technical literature refer to the oxo reaction) is employed for the large-scale preparation of butanol, 2-ethylhexanol, and detergent alcohols. The main use of 2-ethylhexanol is in phthalate esters which are softeners in PVC. The catalysts applied are based on cobalt and rhodium. (For a general review see ref. 3.)... 

The largest group of organic molecular compounds, in which hydrogen bond formation plays no part, are the compounds, usually in the ratio 1 1, between on the one hand aliphatic and aromatic nitro compounds (nitromethane, tetranitro-methane, chloropicrin CC13N02, nitrobenzene, s-trinitrobenzene, picric acid), quinones, anhydrides (phthalic acid-and maleic acid anhydride) and ketones with on the other hand especially aliphatic and aromatic amines (aniline, pyridine), unsaturated aliphatic and aromatic hydrocarbons, ethers etc. 

Palit, 1954), didodecyldimethylammonium halides, and di(2-ethylhexyl)ammo-nium halides. Since many POE nonionics are soluble in aliphatic and aromatic hydrocarbons, structural limitations on the use of these materials for this purpose are not as restrictive as in the case of ionics. Polyanionic soaps made by copolymerization of maleic anhydride and dodecyl (or octadecyl) vinyl ether followed by treatment with morpholine have been used to solubilize water into nonaqueous solvents (Ito, 1964). 

Finally vanadia catalysts are used extensively for oxidations of aromatic hydrocarbons. With bei zene, the mechanism for ring breakage is not well defined, and the desorption of maleic anhydride itself appears to be ratecontrolling. For the oxidation of o-xylene, the use of supported vanadia-titania catalysts limits ring cleavage. A well-defined major product sequence, o-xyltne o-tolualdehyde o-toluic acid phthalide phthalic anhydride... 

Higher molecrolar weight polynuclear aromatic hydrocarbons (PAHs) containing the anthracene nucleus have also been found to react with maleic anhydride. These ring systems, however, can differ widely in reaction rates. Typical examples of those systems that undergo the Diels-Alder reaction are 1,2,5,6-dibenzanthracene (a), 2,3,6,7-dibenzanthracene (pentacene) (b), and 9,10-diphenylanthracene (c). 

The V-Mo-O oxides are well-known industrial catalysts for the synthesis of acrylic acid from acrolein and maleic anhydride from benzene more recently, V-P-0 systems are being utilized for maleic anhydride production from -butane. The V20s/Ti02 combination was employed for phthalic acid production from o-xylene. V-Fe-O catalyzes oxidation of polycyclic aromatic hydrocarbons to dicarboxylic acids and quinones. Methyl formate is produced by the oxidation of methanol over V-Ti-0 catalysts [58]. For many of these processes, it has been experimentally proved that the catalytic reaction follows a Mars-van Krevelen mechanism. The surface coverage with active oxygen 0 in the steady state of the redox reaction following Mars-van Krevelen mechanism is given by... 

Poly(maleic anhydride), prepared with free-radical initiators, is a low molecular weight, creamy white material soluble in water, dilute alkali, ketones, acetonitrile, lower alkyl alcohols, esters, and nitroalkanes. Nonsolvents include aromatic hydrocarbons and most chlorinated compounds. The... 

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