Acenaphthene, oxidation

Acenaphthene oxide is known to be unstable under acidic conditions and is therefore isolated in low yields when prepared by common methods. The highly strained acenaphthene was smoothly epoxidized in quantitative yield at —30°C in CH3CN by using 51 . C -stilbene was epoxidized with 51 at —35 °C in CH3CN to a mixture of the trans-(70%) and c/3-epoxides (30%) (equation 79). This result shows that the peroxysulfonyl intermediate must be a radical like the acylperoxy radical ArC(0)00 ° and the phenyl nitroso oxide radical PhNOO . ... 

A new route to pleiadienes involves photoaddition of maleic anhydride derivatives to acenaphthene, oxidative removal of the anhydride groups, and ring-opening of the resulting cyclobutenes (Scheme 18). Schmidt has reported further details of the synthesis of optically active tricarbonyl(cyclobutadiene)iron complexes, the first step involving [2 + 2] addition of 1,2-dichloroethylene to dichloromaleic anhydride. 

Dehydrogenated intermediates can be formed up to very high conversions. For instance, acenaphthene oxidation gives rise to acenaphthylene as an intermediate of reaction. The selectivity to acenaphthylene is still 20% at a 40% conversion of acenaphthene over Pt. 

Naphthalimides are prepared from naphthaUc anhydride obtained from naphthalene-1,8-dicarboxyhc acid, ie, the oxidation product of acenaphthene or its derivatives, by reaction with amines. They are utilized for synthetic fibers such as polyesters. 

The anhydride can be made by the Hquid-phase oxidation of acenaphthene [83-32-9] with chromic acid in aqueous sulfuric acid or acetic acid (93). A postoxidation of the cmde oxidation product with hydrogen peroxide or an alkaU hypochlorite is advantageous (94). An alternative Hquid-phase oxidation process involves the reaction of acenaphthene, molten or in alkanoic acid solvent, with oxygen or acid at ca 70—200°C in the presence of Mn resinate or stearate or Co or Mn salts and a bromide. Addition of an aHphatic anhydride accelerates the oxidation (95). 

The anhydride of 1,8-naphthalenedicarboxyHc acid is obtained in ca 95—116 wt % yield by the vapor-phase air-oxidation of acenaphthene at ca 330—450°C, using unsupported or supported vanadium oxide catalysts, with or without modifiers (96). 

For example, 5,6-acenaphthenedicarboximide (44) can be prepared in 84% yield by the reaction of acenaphthene with excess sodium cyanate in anhydrous HF (78). The intermediate can be oxidized to the tetracarboxyhc acid. 

The degradation of acenaphthene is initiated by benzylic monooxygenation, and the pathway was determined using [l- C]acenaphthene by the isolation of intermediate metabolites (Selifonov et al. 1998). Importantly, the method proved applicable even when only limited biotransformation of the substrates had taken place by partial oxidation. 

The naphthalimide 11.23 is manufactured from acenaphthene by sulphonation, oxidation to the naphthalic anhydride derivative and conversion to 4-methoxy-N-methylnaphthal-imide as outlined in Scheme 11.14. 

Larger quantities (50-100 g.) of acenaphthene can be oxidized conveniently, but it is very difficult to extract all the quinone from the crude material. If larger quantities are oxidized, the product should be divided into small lots as described above for the bisulfite extraction. The yield is determined to a large extent by the thoroughness of the extraction. 

The naphthalic anhydride (4-11 g.) is recovered on acidification of the filtrate. This substance is the principal product if the oxidation becomes too vigorous. Naphthalic anhydride may be prepared from the technical grade of acenaphthene. 

Hemoglobin is another heme-containing protein, which has been shown to be active towards PAH, oxidation in presence of peroxide [420], This protein was also modified via PEG and methyl esterification to obtain a more hydrophobic protein with altered activity and substrate specificity. The modified protein had four times the catalytic efficiency than that of the unmodified protein for pyrene oxidation. Several PAHs were also oxidized including acenaphthene, anthracene, azulene, benzo(a)pyrene, fluoranthene, fluorene, and phenanthrene however, no reaction was observed with chrysene and biphenyl. Modification of hemoglobin with p-nitrophenol and p-aminophenol has also been reported [425], The modification was reported to enhance the substrate affinity up to 30 times. Additionally, the solvent concentration at which the enzyme showed maximum activity was also higher. Both the effects were attributed to the increase in hydrophobicity of the active site. 

Nitro polycyclic aromatic hydrocarbons are environmental contaminants which have been detected in airborne particulates, coal fly ash, diesel emission and carbon black photocopier toners. These compounds are metabolized Tn vitro to genotoxic agents through ring oxidation and/or nitroreduction. The details of these metabolic pathways are considered using 4-nitrobiphenyl, 1- and 2-nitronaphthalene, 5-nitro-acenaphthene, 7-nitrobenz[a]anthracene, 6-nitro-chrysene, 1-nitropyrene, 1,3-, 1,6- and 1,8-dinitro-pyrene, and 1-, 3- and 6-nitrobenzo[a] pyrene as examples ... 

Naphthalic acid imide 69 is obtained through air oxidation of acenaphthene 72 with vanadium peroxide as a catalyst. The intermediate, naphthalic anhydride 73, is subsequently reacted with ammonia ... 

The acid, referred to as tetra acid , is prepared as follows In a Friedel-Crafts reaction, acenaphthene 72 is reacted with malonic dinitrile and aluminum chloride. The resulting condensation product 75 is oxidized with sodium chlorate/hy-drochloric acid to form the dichloroacenaphthindandione 76. Oxidation with sodium hypochlorite solution/sodium permanganate affords naphthalene tetracar-boxylic acid 68, mostly existing as the monoanhydride 68a. The dianhydride, on the other hand, evolves only after drying at approx. 150°C. 

Chemical/Physical. Ozonation in water at 60 °C produced 7-formyl-1-indanone, 1-indanone, 7-hydroxy-l-indanone, l-indanone-7-carboxylic acid, indane-l,7-dicarboxylic acid, and indane-1-formyl-7-carboxylic acid (Chen et al, 1979). Wet oxidation of acenaphthene at 320 °C yielded formic and acetic acids (Randall and Knopp, 1980). The measured rate constant for the gas-phase reaction of acenaphthene with OH radicals is 8.0 x 10 " cmVmolecule-sec (Reisen and Arey, 2002). 

Schocken, M.J. and Gibson, D.T. Bacterial oxidation of the polycyclic aromatic hydrocarbons acenaphthene and acenaphthylene, AppL Environ. Microbiol, 48(1) 10-16, 1984. 

The major oxidation product isolated was anthracene, perhaps formed in part from the hydroperoxide (I). However, significant amounts of potassium superoxide accompanied the anthracene. This result suggests that the major source of anthracene involved the oxidation of the dianion. In pure DMSO in the presence of excess potassium tert-butoxide, a trace of oxygen converts 9,10-dihydroanthracene, 9,10-dihy-drophenanthrene, or acenaphthene to the hydrocarbon radical anions. These products are apparently formed in the oxidation of the hydrocarbon dianions. 

Acenaphthenol has been prepared in poor yield by the oxidation of acenaphthene with lead dioxide 2 and it is among... 

More recent work by Hopff and Koulen 0 further broadened the scope of the reaction by including an assortment of dieubstituted benzenes, and also biphenyl and acenaphthene. Somerville and Spoerri,1 05-1 4 moreover, have examined the action of isobutylene oxide and 2,3-epoxybutane on benzene in the presence of aluminum chloride Mixtures of alcohols and hydrocarbons were isolated, as in previous work. 

Chemically, creosote is a mixture of a great number of compounds, almost exclusively of cyclic structure. Individual compounds present in creosote in concentrations of 2-4% are acenaphthene, fluorene, diphenylene oxide, anthracene, and carbazole. Only one compound, phenanthrene, is present in a larger concentration (12-14%). For many years, chemists in many countries have tried tu isolate individual compounds and to find profitable uses for them. Most of these attempts have failed with exception of those involving anthracene. See also Anthracene. The principal use of creosote is for preservation of wood. Railroad lies, poles, fence posts, marine pilings, and lumber for outdoor use are impregnated with creosote in large cylindrical vessels. If properly treated, the life of the wood is greatly extended. Materials that are competitive with creosote for wood-preservation purposes include various petroleum oils, and pentachlorophenol. Pentachlorophenol is used in solutions of creosote or of petroleum oils. Blends of creosote with petroleum oils also are used for economic reasons. 

Acenaphthene. (CAS 83-32-9]. Acenaphthene is a hydrocarbon, C12H10, present in high temperature coal tar. Acenaphthene may be halogenated. sulfonated. and nitrated in a manner similar to naphthalene. Oxidation first yields acenaphthenequmone, followed by 1.8-naphthalenedicarboxyhc acid anhydride and pesticides. 

A radical chain oxidation mechanism, involving the formation and decomposition of an intermediate hydroperoxide, is consistent with the observed kinetics in the oxidation of cumene and acenaphthene by oxygen in the presence of alkylammonium perchlorates.128... 

Beltran et al. (1996a) investigated the advanced oxidation of the aqueous solution of three polynuclear aromatic hydrocarbons (PAHs) fluorene, phenanthrene, and acenaphthene. The oxidative mechanism of substrates by 03 alone, 03 combined with H202, UV radiation (254 nm) alone, or a combination of UV/H202 has been analyzed. In addition, the influence of different water sources, such as surface and organic-free waters, and type of occurring oxidation was also studied. 

The naphthalimide ring system has the drawback of low effectiveness, which is mainly attributable to the low molar extinction coefficient. The industrial synthesis of alkoxynaphthalimides begins with acenaphthene. Chlorination and subsequent oxidation with dichromate give the corresponding naphthalic acids [116], which are converted to the anhydrides on drying. Mild reaction with methyla-mine, followed by reaction with sodium methoxide or sodium ethoxide, gives, e.g., 64 or 65. 

Tar Fluorene Diphenylene oxide Acenaphthene Methyl-naphthalenes... 

Carbon/silica adsorbents with pure or functionalized carbon deposits, or functionalized silica surfaces, are of interest for many purposes, An improvement of the structural and adsorption characteristics of carbon deposits is desirable.1 Pyrocarbon deposits formed by carbonization of low-molecular organic precursors (dichloromethane, cyclohexene, alcohols, acetylacetone, acenaphthene, etc) at oxide surfaces typically possess a low inner specific... 

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