Benzene and naphthalenes, alkylated

These conclusions were not applicable when sediment was the source of hydrocarbons. McCain et al. (5) studied the bioavailability of petroleum in sediment to English sole (Parophrys vetu-lus). Sediments rich in alkylated and non-alkylated benzenes and naphthalenes, together with fluorene and phenanthrene, were employed. After 11 days of exposure, samples of skin, muscle, and liver were examined. Fluorene and phenanthrene were not accumulated in the test fish however, significant concentrations of 1-methyl naphthalene, 2-methyl naphthalene, 2,6-dimethyl naphthalene and 1,2,3,4-tetramethylbenzene, were found in skin and liver (Table II) 1-methyl naphthalene and 2-methyl naphthalene were the major components of muscle. In each tissue examined, 1-methyl-naphthalene was the major component 1,2,3,4-tetramethylbenzene occurred in relatively low concentrations in skin and muscle in comparison to naphthalenes containing one and two alkyl groups. 

Figure 11.5 shows that the functional group compositional analysis of the pyrolysis oil/waxes derived from the fixed-bed pyrolysis of PVC, PS and PET is very different from the polyalkene plastic pyrolysis oil/waxes. The spectra of the PVC pyrolysis oil/wax shows that the characteristic peaks of alkanes and alkenes are present as described for the polyalkene plastics. Since the PVC plastic polymer is based on a similar backbone structure to the polyalkene plastics, a similar degradation product oil/wax composition may be expected. However, the spectra for PVC in Figure 11.5 show that there are additional peaks in the region of 675-900 cm and 1575-1625 cm The presence of these peaks indicates the presence of mono-aromatic, polycyclic aromatic and substituted aromatic groups. Benzene has been identified as a major constituent in oils derived from the pyrolysis of PVC whilst other aromatic compounds identified included alkylated benzenes and naphthalene and other polycyclic aromatic hydrocarbons [19, 32, 39]... 

Chemically, kerosene is a mixture of hydrocarbons, and the constituents include n-dodecane n-Ci 2, alkyl benzenes, and naphthalene and its derivatives (ASTM D-1840). The chemical composition depends on its source and has a high number (>100,000) of isomers that are possible (Table 7.2). The actual number of compounds in kerosene is much lower, and there are claims to less than 100 constituents but that, again, is source- and process dependent. 

Ziircher and Thiier (32), in a recent paper, examined the effects of suspended solids (kaolinite) on the weathering of a No. 2 fuel oil by GC and IR. They found that there was fractionation of the oil with alkylated benzenes and naphthalenes enriched in the water phase while aliphatic hydrocarbons (above MW 250) were adsorbed. They also found that with increased turbulence, oil droplets were agglomerated with suspended minerals. They observed the same fractionation pattern for a ground-water oil spill, despite the fact that the oil had been biochemically altered. 

The reactions outlined in the previous sections all utilized an arene with a heteroatom substituent that could stabilize the arenium intermediates resulting from electrophilic addition. Benzene, alkylated benzenes, and naphthalene are more difficult to activate because they lack this mode of stabilization. Osmium... 

Emissions from the consumption of diesel fuel are low, however. There is virtually no evaporation. In 1969, hydrocarbon emissions from diesel-powered vehicles in the USA amounted to 200,000 t (as compared with 16.9 million t from gasoline engined vehicles) [13]. Of this figure, the Cio-C24-hydrocarbons account for a relatively low portion, but are nevertheless responsible for the offensive odour [13]. A few hundred different components have been found, some are components of the diesel oil but others are formed by combustion [13]. The more important constituents are indanes, tetralines, alkyl benzenes, naphthalenes, indoles, acenaphthenes, and benzothiophenes [13]. It appears that the quantitatively less important aromatic aldehydes and ketones are responsible for the odour [13]. At a rough estimate, the total world emissions of alkyl benzenes and naphthalenes must amount to some 200,000 t. Diesel particulate emissions contain neutral fractions with microbial mutagenic activity [26 a]. 

Most of the naphthalene produced is oxidized to phthalic anhydride [2, 36]. In addition, naphthalene is used as the basis for other intermediates - primarily as initial products for dyestuffs - [36], or it is used besides and with p-dichlorobenzene as mothproofing agent and insecticide. Products similar to diesel oil - such as Aerotox 3470 - together with alkylated benzenes and naphthalenes are also used as solvents for pesticides, and are then introduced into the environment by spraying [44]. 1,1-phenyl-xylyl-ethane and diisopropyl naphthalene are PCB substitutes [45]. 

Reactions other than those of the nucleophilic reactivity of alkyl sulfates iavolve reactions with hydrocarbons, thermal degradation, sulfonation, halogenation of the alkyl groups, and reduction of the sulfate groups. Aromatic hydrocarbons, eg, benzene and naphthalene, react with alkyl sulfates when cataly2ed by aluminum chloride to give Fhedel-Crafts-type alkylation product mixtures (59). Isobutane is readily alkylated by a dipropyl sulfate mixture from the reaction of propylene ia propane with sulfuric acid (60). 

C-Alkylations may be discussed under the headings of alkene reactions and A/-alkyl rearrangements. The isopropylation of benzene and naphthalene are two important examples of alkylation with alkenes (see Alkylation). Manufacture of j butylaniline, by heating /V-butylaniline with 2inc chloride, typifies the rearrangement reaction appropriate to and higher alkyl derivatives. 

The procedure used in the preceding sections for cyclopropane serves equally well in the analytic determination of the numbers of structure and stereoisomeric compounds which obtain when essentially different radicals of valence one or alkyl radicals are substituted in the basic compound. We have to assume, however, that there is enough information on the basic compound to determine the three groups discussed in Sec. 56. This is certainly the case for the most important basic compounds, benzene and naphthalene. I omit the formulation of rules which are obvious in the preceding example. 

Including aromatic amines (to be discussed below) the order of reactivities for substituted benzene and naphthalene coupling components is therefore O" > NR2 > NHR > NH2 > OR = OH > CH3 > unsubstituted (R = alkyl). 

Friedel-Crafts alkenylation of arenes with various phenylacetylenes to yield 1,1-diarylalkenes was reported. Alkyl-substituted benzenes and naphthalene react with phenylacetylene in the presence of zeolite HSZ-360 to afford the products in good to excellent yields and selectivities 415... 

Industrial effluents Organic compounds chloro- and nitrophenols, nonionic surfactants, linear alkylated benzene sulfonates, benzene and naphthalene sulfonates, estradiol, ethinyl estradiol V. fischeri (ToxAlert 10, ToxAlert 100) There were certain correlations between the results of the chemical analyses and bioassays to a large extent, however, the composition of the samples remained unknown Distinct correlations were found between the inhibition of bioluminescence and compound content, but only in the case of nonylphenol, nonylphenol carboxylate, nonylphenol ethoxylate, and chlorophenols 84... 

Substrates of Friedel-Crafts acylations are benzene and naphthalene, as well as their halogen, alkyl, aryl, alkoxy, or acylamino derivatives. Acceptor-substituted aromatic compounds are inert. Because Friedel-Crafts acylations introduce an acceptor into the aromatic substrate, no multiple substitutions take place. This distinguishes them from Friedel-Crafts alkylations. Free OH and NH2 groups in the aromatic compound prevent Friedel-Crafts acylations because they themselves are acylated. However, the O-acylphenols available in this way can later be rearranged with A1C1, into orf/zo-acylated isomers (Fries rearrangement). 

The reaction can be smoothly applied to a broad variety of alkyl-substituted benzene and naphthalene derivatives 2,3-dimethyl-, 2,5-dimethyl-, or 2,3,5,8-tetramethylnaphthalene and l-hydroxy-2-methylnaphthalene are converted by CH3Re03/H202 in good to excellent yields (60-100 %) see Table 1 and eqs. (1) and (2) [7, 8]. 

Hydeal HOP Toluene, xylenes and other alkyl benzenes heavy reformate, from rerun catalytic reformate, light cycle oil from cat. Cracking A catalytic process for making benzene and naphthalene... 

THD Gulf Oil Corporation Toluene, xylenes and other alkyl benzene fractions Benzene and naphthalene... 

Series of halo- and alkyl-substituted benzene- and naphthalene-sulfonamides have been obtained by this method. 

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