Naphthalene oxidation data

Summary of Nonlinear Fitting of Naphthalene Oxidation Data... 

For fitting such a set of existing data, a much more reasonable approach has been used (P2). For the naphthalene oxidation system, major reactants and products are symbolized in Table III. In this table, letters in bold type represent species for which data were used in estimating the frequency factors and activation energies contained in the body of the table. Note that the rate equations have been reparameterized (Section III,B) to allow a better estimation of the two parameters. For the first entry of the table, then, a model involving only the first-order decomposition of naphthalene to phthalic anhydride and naphthoquinone was assumed. The parameter estimates obtained by a nonlinear-least-squares fit of these data, are seen to be relatively precise when compared to the standard errors of these estimates, s0. The residual mean square, using these best parameter estimates, is contained in the last column of the table. This quantity should estimate the variance of the experimental error if the model adequately fits the data (Section IV). The remainder of Table III, then, presents similar results for increasingly complex models, each of which entails several first-order decompositions. 

The effect of solvent on the rate, E, and dS can be derived from the data on haloquinolines and their A-oxides (Tables X and XI), on halonitronaphthalenes (Tables XII and XIII), and on halodinitro-naphthalenes (Table XVI). Depending on the nature of the reaction, the relative reactivity of two compounds can be substantially different in different solvents. For example, piperidination of 2-chloroquinoline (Table X, lines 3 and 4) compared to 2-chloroquinoxaline (Table XV,... 

The data in Figure 5 indicates that the presence of the naphthalene chromophore does not prevent the decrease in contact angle observed upon the irradiation of PVCa. Thus, naphathalene may rot be an effective quencher of the surface oxidation of PVCa film as it appears to be for the yellowing of PVCa in solution. 

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 gas-phase air oxidation of hydrocarbons (o-xylene and/or naphthalene) to phthalic anhydride (PA) is carried out in multitubular reactors. The tubes are filled with a catalyst, whereas molten salts are recirculated in the intertubular space. This mode of operation makes it possible to carefully control conditions of the reaction, with the efficient removal of heat and the high yield of PA. The improvement in the design of the reactors and the introduction of a new generation of catalysts led to a considerable increase in productivity with a simultaneous decrease in the costs of production. Unfortunately, the intensification of the process diminished the lifespan of the catalysts. Based on the experience of PA manufacturers [1] the following data may be quoted (Table I) ... 

Isoquinoline is more reactive at the 1-position than quinoline is at the 2-position by approximately the same factor by which the 1-position of naphthalene is more reactive than the 2-position this is true also for the N-oxides. Comparison of the rate data for quinoline and quinoxaline (11.15), and the data in 11.59, suggests that replacement of =CH— by =N— accelerates the exchange at the 2- and 3-positions by factors of 135 and 20, respectively. The low reactivity of quinoxaline N-oxide seems anomalous and may be in error. 

SAFETY PROFILE Confirmed carcinogen with experimental tumorigenic data by skin contact. Human systemic effects by inhalation unspecified effects on olfaction and respiratory systems. Corrosive effects on the skin, eyes, and mucous membranes by inhalation. Flammable when exposed to heat or flame. Will react with water or steam to produce heat and toxic and corrosive fumes. Violent or explosive reaction with dimethyl sulfoxide, and aluminum chloride + naphthalene. To fight fire, use alcohol foam, CO2, dry chemical. Incompatible with dimethyl sulfoxide, (NaNs + KOH), water, steam, and oxidizers. When heated to decomposition it emits toxic fumes of CT, See also CHLORIDES and ALDEHYDES. 

The selective oxidation reaction is carried out in excess air so that it can be considered pseudo-first-order with respect to naphthalene. Analysis of available data indicates that the reaction rate per unit mass of catalyst is represented by ... 

In the oxidation of the naphthalene ring then, it is seen that three types of reactions are controlling First, the addition of oxygen to the ring, second, the destruction of the naphthalene ring, and third, the destruction of the benzene ring. Theoretically, it should be possible to stop at any of the intermediate steps but actually only the points of major resistance may be depended upon to allow isolation of intermediate oxidation products. From the existing data it is impossible to determine the reaction rates of the different steps and the presence of catalysts would make any ordinary presentation difficult even with more data than are available.28... 

That aluminum oxide is but an inactive catalyst toward the oxidation is shown by the experimental data obtained with it. When a mixture of one part of naphthalene with 16 parts of air by weight is passed through a tube containing aluminum oxide maintained at about 450° C. at such a rate that the time of contact is about 0.4 second, a yield of only 12.5 parts of phthalic anhydride and 5 parts of naphthaquinone per 100 parts of original naphthalene is obtained.42... 

A striking illustration of the relative stability of the benzenoid and of a hydroaromatic ring is afforded by the oxidation of tetra-hydro-naphthalene with air. The preponderating product is phthalic anhydride, with little or no tetrahydronaphthalic acid present, showing the selectively complete destruction of the non-benzenoid ring. Data on the oxidation of tetrahydronaphthalene are available from the work of Maxted,J7 and are shown in Table XLI. 

Salicylic Acid. 2-Hydmxybenimc acid Keralyt Verrugon. C,H(03 mol wt 138.12. C 60.87%. H 4.38%. O 34.75%. Occurs in the form of esters in several plants, notably in wintergreen leaves and the bark of sweet birch. Made synthetically by heating sodium phenolate with carbon diox -ide under pressure. Large scale process details Faith et at. Industrial t hem [cats (Wiley, New York, 3rd ed.. 1965) pp 652-655. Novel method by microbial oxidation of naphthalene Zajic, Dunlap. U.S. pat. 3,274,074 (1966 to Kcrr-McGee). Toxicity data K. Sota et at. J. Pharm. Soc. Japan 89, 1392 (1969). 

Baneijee et al.66 have developed an alternative synthesis of the compound (129) whose utility in synthesis of Mansonone F (120) has been reported by Suh and collaborators.65 This is described in Scheme 13. Tetralone (127) was reduced with sodium borohydride to alcohol which on alkylation with benzyl chloride produced benzyl derivative (132). Its conversion to (133) was attempted by treatment with boron tribromide in dichloromethane. C ompound (133) (characterized b y m ass s pectroscopy) was obtained in poor yield. The major product was the diol (134), whose structure was confirmed by spectral data. It indicates that the demethylation was accompanied by debenzylation. Treatment of diol (134) with triethyl orthoformate and aluminium chloride afforded aldehyde (135) which was subjected to catalytic hydrogenation to produce compound (136). It was transformed to ketone (137) by oxidation and then made to react with methylmagnesium bromide in ether. The resulting tertiary alcohol on heating with p-toluenesulfonic acid in toluene for 24 hr produced the naphthalene (129) in 78% yield. 

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