Tetralin oxidation

Tn 1955 Russell showed that mixtures of cumene and small amounts of - Tetralin oxidized at rates considerably below the rates of oxidation of either of the pure hydrocarbons (26). Russell suggested that this decrease in rate was caused by the fact that tetralylperoxy radicals terminate oxidation chains much more readily than cumylperoxy radicals. The mixtures, therefore, oxidize at a lower rate than pure cumene because of... 

The effectiveness of dibenzylhydroxylamine as a inhibitor of AIBN-initiated tetralin oxidation can be seen from the data in Figure 6. A comparison between dibenzylhydroxylamine and butylated hydroxytoluene (BHT) can be made from those data. The lower rate of oxygen consumption in the solution containing dibenzylhydroxyl-... 

Figure 6. Inhibition of tetralin oxidation by dibenzylhydroxyl amine, AIBN-inhibited.

More recently, Farrusseng and coworkers [119] described the encapsulation of large metal phthalocyanine (MPc) in the cavities of MIL-101 for the selective oxidation of tetrahn into 1-tetralone, a diesel fuel additive and an intermediate for the synthesis of agricultural chemicals (Figure 10.18). After a catalytic screening of different rmsupported metal phthalocyanine catalysts in aerobic tetralin oxidation, the MPc-MOF composite materials were prepared by wet infiltration of MPc... 

Figure 10.18 Conversion (solid line) and selectivity (dashed line) of MIL-101-encapsulated Fe—phthalocyanine for tetralin oxidation.

Thus the syntheses of the nitrogen analogue of tetralin oxide (219) and the steroidal aziridines (220) and (221) have all been achieved in good yield. 

Jiang D, Mallat T, Krumeich F, Baiker A. Metal organic frameworks (MOFs) as catalysts a combination of Cu " and Co " MOFs as an efficient catalyst for tetralin oxidation. J Catal 2008 257 390-5. 

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). 

Tetracyanobenzoquinone [4032-03-5] 3,6-dioxo-l,4-cyclohexadiene-l,2,4,5-tetracarbonitrile, is a remarkably strong oxidizing agent for a quinone it abstracts hydrogen from tetralin or ethanol even at room temperature (50). It is a stronger TT-acid than TCNE because it forms more deeply colored TT-complexes with aromatic hydrocarbons. 

The benzylic position in tetralin can be selectively oxidized to the hydroperoxide... 

However, this oxidation to carbonyl failed with the complexes of tetralin, o-chlorotoluene, 9,10-dihydrophenanthrene, and acenaphthalene [109]. The aniline complex can be oxidized to the nitrobenzene complex using H202 in CF3C02H [86] Eq. (38). This reaction parallels the analogous oxidation of aminocobaltici-nium [86, 111],... 

The catalytic system used in the Pacol process is either platinum or platinum/ rhenium-doped aluminum oxide which is partially poisoned with tin or sulfur and alkalinized with an alkali base. The latter modification of the catalyst system hinders the formation of large quantities of diolefins and aromatics. The activities of the UOP in the area of catalyst development led to the documentation of 29 patents between 1970 and 1987 (Table 6). Contact DeH-5, used between 1970 and 1982, already produced good results. The reaction product consisted of about 90% /z-monoolefins. On account of the not inconsiderable content of byproducts (4% diolefins and 3% aromatics) and the relatively short lifetime, the economics of the contact had to be improved. Each diolefin molecule binds in the alkylation two benzene molecules to form di-phenylalkanes or rearranges with the benzene to indane and tetralin derivatives the aromatics, formed during the dehydrogenation, also rearrange to form undesirable byproducts. 

Polymer-supported catalysts often have lower activities than the soluble catalysts because of the intraparticle diffusion resistance. In this case the immobilization of the complexes on colloidal polymers can increase the catalytic activity. Catalysts bound to polymer latexes were used in oxidation reactions, such as the Cu-catalyzed oxidation of ascorbic acid,12 the Co-catalyzed oxidation of tetralin,13 and the CoPc-catalyzed oxidation of butylphenol14 and thiols.1516 Mn(III)-porphyrin bound to colloidal anion exchange resin was... 

Autoxidation may in some cases be of preparative use thus reference has already been made to the large-scale production of phenol+ acetone by the acid-catalysed rearrangement of the hydroperoxide from 2-phenylpropane (cumene, p. 128). Another example involves the hydroperoxide (94) obtained by the air oxidation at 70° of tetrahydro-naphthalene (tetralin) the action of base then yields the ketone (a-tetralone, 95), and reductive fission of the 0—0 linkage the alcohol (a-tetralol, 96) ... 

Howard and Ingold studied this equilibrium reaction in experiments on the oxidation of tetralin and 9,10—dihydroanthracene in the presence of specially added triphenylmethyl hydroperoxide[41]. They estimated the equilibrium constant K to be equal to 60 atm-1 (8 x 103 L mol-1, 303 K). This value is close to T=25atm-1 at 300 K (A/7=38kJ mol-1), which was found in the solid crystal lattice permeable to dioxygen [84], The reversible addition of dioxygen to the diphenylmethyl radical absorbed on MFI zeolite was evidenced and studied recently by the EPR technique [85],... 

This reaction was proposed in 1960 for compounds with a weak C—H bond [33] and was experimentally proved in the reactions of oxidation of cyclohexanol and tetralin [34,35], The rate of this reaction was found to obey the following equation ... 

The linear co-oxidation dependence was observed for the following pairs of hydrocarbons (333 K, initiator AIBN) tetralin-ethylbenzene, phenylcyclopentane-ethylbenzene, phenyl-cyclohexane-ethylbenzene, tetralin-phenylcyclohexane, cyclohexene-2-butene, 2,3-dimethyl, and cyclohexene-pinane [8]. 

Alkylaromatic hydrocarbons, such as tetralin, ethylbenzene, and cumene, are oxidized in a solution of acetic acid in the presence of cobalt acetate by a different mechanism. In these... 

Aryl phosphites inhibit the initiated oxidation of hydrocarbons and polymers by breaking chains on the reaction with peroxyl radicals (see Table 17.3). The low values of the inhibition coefficient / for aryl phosphites are explained by their capacity for chain autoxidation [14]. Quantitative investigations of the inhibited oxidation of tetralin and cumene at 338 K showed that with increasing concentration of phosphite /rises tending to 1 [27]. 

During the chain oxidation of hydrocarbons, sulfides and disulfides terminate chains by reacting with peroxyl radicals [40,42,44], which, as opposed to phenols, are weak inhibitors (see Table 17.6). The mechanism and stoichiometry of the termination reaction by sulfides remain yet unclear. Since sulfenic acid is an efficient scavenger of free radicals, the oxidation of tetralin in the presence of dialkylsulfoxide occurs only if the initiation rate v > vimin is proportional to the concentration of sulfoxide [5], so that the rate of oxidation is... 

At the end of this period the partially oxidized tetralin is poured into 500 cc. of 2 N sodium hydroxide, with vigorous me-... 

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