Dehydrogenation of aromatics

Remarkably, the same Shvo complex can be used for the catalytic transfer dehydrogenation of aromatic amines to give imines (Scheme 7.14) [80]. This reaction produces high yields when carried out for 2-6 h in refluxing toluene with 2 mol.% catalyst. A quinone is used as the hydrogen acceptor, giving the corresponding hydroquinone. 

The catalytic activity of various semiconducting oxides and mixtures of oxides for the dehydrogenation of aromatic hydrocarbons is increased by ultraviolet irradiation 65>. The carbon monoxide oxidation photosensitized by ZnO has been studied by several authors (see below) 66 70>. 

The mechanism of dehydrogenation of aromatic compounds with dichlorodicyanoquinone (DDQ) is shown in Scheme 7,32. 

Dehydrogenation of aromatic aldoximes to nitrile oxides [1, 80, before references]. N-Bromosuccinimide in dimethylformamide is an excellent reagent for the dehydrogenation of aromatic aldoximes to the corresponding nitrile oxides.17 Triethylamine serves well as base required to bind the hydrogen bromide eliminated since it is... 

Dehydrogenation of aromatic aldoximes.6 Unhindered aromatic nitrile oxides such as benzonitrile oxide (1) dimerize spontaneously to furoxazanes or 1,2,5-oxadiazole-1-oxides (2). If o.o -substituents are present, as in (3), they tend to inhibit dimeriza-... 

Very fine, dense powder with a light brown, coffeelike color reacts with dil. HCl to give chlorine. Its physical state, characterized by small particle size, lattice defects and occlusions of admixtures which prove to be amorphous and on x-ray analysis are recognizable under an ultramicroscope [6], causes an extraordinary high chemical activity. Especially useful in dehydrogenation of aromatic dihydroxy compounds to the correspondii ... 

Scheme 2.176 Peroxidase-catalyzed oxidative dehydrogenation of aromatics...

Alkyl groups attached to aromatic rings are oxidized more readily than the ring in alkaline media. Complete oxidation to benzoic acids usually occurs with nonspecific oxidants such as KMnO, but activated tertiary carbon atoms can be oxidized to the corresponding alcohols (R. Stewart, 1965 D. Arndt, 1975). With mercury(ll) acetate, allyiic and benzylic oxidations are aJso possible. It is most widely used in the mild dehydrogenation of tertiary amines to give, enamines or heteroarenes (M. Shamma, 1970 H. Arzoumanian. 1971 A. Friedrich, 1975). 

Arylation of Aromatic Compounds. In contrast to Friedel-Crafts alkylations, arylations of aromatics are not as well known, and usually require drastic conditions. They iaclude (/) dehydrogenating condensation (SchoU reaction) (2) arylation with aryl haUdes and (J) arylation with dia2onium hahdes. 

The most important process to produce 1-naphthalenol was developed by Union Carbide and subsequently sold to Rhc ne-Poulenc. It is the oxidation of tetralin, l,2,3,4-tetrahydronaphthalene/719-64-2] in the presence of a transition-metal catalyst, presumably to l-tetralol—1-tetralone by way of the 1-hydroperoxide, and dehydrogenation of the intermediate ie, l-tetralol to 1-tetralone and aromatization of 1-tetralone to 1-naphthalenol, using a noble-metal catalyst (58). 1-Naphthol production in the Western world is around 15 x 10 t/yr, with the United States as the largest producer (52). 

Like mthenium, amines coordinated to osmium in higher oxidation states such as Os(IV) ate readily deprotonated, as in [Os(en) (NHCH2CH2NH2)] [111614-75-6], This complex is subject to oxidative dehydrogenation to form an imine complex (105). An unusual Os(IV) hydride, [OsH2(en)2] [57345-94-5] has been isolated and characterized. The complexes of aromatic heterocycHc amines such as pyridine, bipytidine, phenanthroline, and terpyridine ate similar to those of mthenium. Examples include [Os(bipy )3 [23648-06-8], [Os(bipy)2acac] [47691-08-7],... 

Styrene undergoes many reactions of an unsaturated compound, such as addition, and of an aromatic compound, such as substitution (2,8). It reacts with various oxidising agents to form styrene oxide, ben2aldehyde, benzoic acid, and other oxygenated compounds. It reacts with benzene on an acidic catalyst to form diphenylethane. Further dehydrogenation of styrene to phenylacetylene is unfavorable even at the high temperature of 600°C, but a concentration of about 50 ppm of phenylacetylene is usually seen in the commercial styrene product. 

Catalytic Reforming. Worldwide, approximately 30% of commercial benzene is produced by catalytic reforming, a process ia which aromatic molecules are produced from the dehydrogenation of cycloparaffins, dehydroisomerization of alkyl cyclopentanes, and the cycHzation and subsequent dehydrogenation of paraffins (36). The feed to the catalytic reformer may be a straight-mn, hydrocracked, or thermally cracked naphtha fraction ia the... 

The dehydrogenation reaction produces crude styrene which consists of approximately 37.0% styrene, 61% ethylbenzene and about 2% of aromatic hydrocarbon such as benzene and toluene with some tarry matter. The purification of the styrene is made rather difficult by the fact that the boiling point of styrene (145.2°C) is only 9°C higher than that of ethylbenzene and because of the strong tendency of styrene to polymerise at elevated temperatures. To achieve a successful distillation it is therefore necessary to provide suitable inhibitors for the styrene, to distil under a partial vacuum and to make use of specially designed distillation columns. 

The generation of caibocations from these sources is well documented (see Section 5.4). The reaction of aromatics with alkenes in the presence of Lewis acid catalysts is the basis for the industrial production of many alkylated aromatic compounds. Styrene, for example, is prepared by dehydrogenation of ethylbenzene made from benzene and ethylene. 

Dehydrocyclization refers to the conversion of feed paraffins into alkylcyclohexane and alkylcyclopentane naphthenes. These, in turn, are subsequently converted by isomerization and dehydrogenation into aromatics. Dehydrocyclization is controlled by both acid and platinum functions and is the most sensitive indicator of catalyst selectivity. 

The intermediacy of dipolar species such as 186 has been demonstrated by reaction of enamines with 2-hydroxy-1-aldehydes of the aromatic series (129). The enamine (113) reacts in benzene solution at room temperature with 2-hydroxy-1-naphthaldehyde to give the crystalline adduct (188) in 91 % yield. Oxidation with chromium trioxide-pyridine of 188 gave 189 with p elimination of the morpholine moiety. Palladium on charcoal dehydrogenation of 189 gave the known 1,2-benzoxanthone (129). 

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