Oxidation of acenaphthene

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). 

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 ... 

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). 

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

The oxidizing agent employed is not very powerful, and, although it attacks easily the particularly reactive anthracene, it is not suitable for the conversion of hydrocarbons of the naphthalene and phenanthrene series into the corresponding quinones or for the oxidation of acenaphthene or fluorgne (observation of the checkers). 

For example, oxidation of acenaphthene by red lead in acetic acid gives 7-acenaphthenol acetate, from which 7-acenaphthenol is obtained by saponification with methanolic sodium hydroxide. Phenols may be prepared indirectly from aromatic aldehydes by oxidation with peracetic acid followed by hydrolysis of the resulting aryl formate. "... 

Anthracene was oxidized to anthraquinone by warming a mixture of 90 g. of finely powdered hydrocarbon, 0.5 g. of vanadium pentoxide, 76 g. of sodium chlorate, 1 1. of acetic acid, and 200 ml. of 2% sulfuric acid under reflux until a vigorous reaction set in. After eventual brief refluxing, anthraquinone was obtained in 88-91% yield. The method is not suitable for the oxidation of hydrocarbons of the naphthalene or phenanthrene series to the quinones or for oxidation of acenaphthene or fluorene. 

C Johannes, A Majcherczyk, A Huttermann. Oxidation of acenaphthene and acenaphthylene by laccase of Trametes versicolor in a laccase-mediator system. J. Biotech. 61(2) 151-156, 1998. 

Figure 10.1 Flow diagram of the gas-phase oxidation of acenaphthene...

The A-hydroxyphthalimide (NHP)-catalysed oxidation of acenaphthene by molecular O2 in chlorobenzene has been studied using 2,2 -azobisisobutyronitrile (AIBN)... 

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. 

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. 

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. 

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. 

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. 

Polycyclic quinones are prepared by careful oxidation of the corresponding hydrocarbons with chromic-sulfuric acid mixture in acetic acid solution or as an agitated aqueous suspension, e.g., 2,3-dimethy 1-1,4-naphthoquinone (80%), 9,10-phenanthroquinone (80%), and acenaphthene-quinone (60%). A laboratory reactor has been described in which an acetic acid solution of chromic acid and another solution of hydrocarbon are mixed as a film at 90°. The reaction mixture is then fed into water to prevent ftirther oxidation. By this procedure, the yield of 2-methyl-1,4-naphthoquinone has been raised from 29% by the usual process to... 

The half-life of acenaphthene in the bluegill fish is less than 1 day. A Beijerinckia species and a mutant strain, Beijerinckia species strain B8/36, were shown to oxidize acenaphthene. Both organisms oxidize acenaphthene to the same spectrum of metabolites, which included 1-acenaphthenol, 1-acenaphthene-one, 1,2-acenaphthenediol, acenaphthenequinone, and a compound that was tentatively identified as 1,2-dihydroxyacenaphthylene. 

Solvent or fractional condensation methods, however, do not give complete separation from the anthracene of such substances as acridine, Ruorantln-enc, flnorene, pyrene, methyl-anthracene, chrysene, acenaphthene, high molecular weight paraffin hydrocarbons, etc., which are present in the crude anthracene press cake. During the subsequent oxidation of anthracene by the liquid phase method these substances result in the formation of impurities difficult to separate from the anthraquinoue and detracting considerably from its quality as a dye intermediate. 

Acenaphthene. The catalytic vapor phase oxidation of ace-naphthene results in the formation of a variety of products such as acenaphthylene, aceuaplithoquinone, naphthaldehydic add, naphthalic anhydride, maldc acid, etc.48 Catalysts similar to those used in the oxidation of anthracene... 

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