Toluene, alkylation xylenes

Benzene is a flammable liquid and its vapors are toxic and explosive. Low concentrations are dangerous on continued inhalation because benzene affects the blood forming function of the bone marrow and it is a cancirogen. Dermatitis may result from repeated skin contact. Alkyl derivatives such as toluene and xylenes are far less toxic and are, therefore, much safer than benzene for use in solvents. Some of the symptoms of benzene poisoning are dizziness, constriction of the chest, and tightening of the leg muscles. 

Thiation was most frequently carried out in pyridine - for unsubstituted compounds which are considerably polar, this is a prerequisite. The less polar iV-alkylated derivatives can be thiated in toluene or xylene for thiation of 6-azathymine, tetralin was also used. ... 

Ar-Alkylations of 5//-dibenz[6,/]azcpines, e.g. 5 > 8 can be readily achieved via their nitranions, which are generated from the NH compounds by standard methodology, e.g. with sodium hydride, or sodamide, in refluxing toluene or xylene.30-J1-bt, 7° 124,1 s2 Occasionally, dioxane,187 or a mixture of tetrahydrofuran and hexamethylphosphoric triamide is used as solvent.137... 

Figure 10.7 Pora-selectivity as a function in the conversion of the alkylation of methanol and toluene to xylene by bare and silicalite-coated H—ZSM5 catalyst particles.

Since their development in 1974 ZSM-5 zeolites have had considerable commercial success. ZSM-5 has a 10-membered ring-pore aperture of 0.55 nm (hence the 5 in ZSM-5), which is an ideal dimension for carrying out selective transformations on small aromatic substrates. Being the feedstock for PET, / -xylene is the most useful of the xylene isomers. The Bronsted acid form of ZSM-5, H-ZSM-5, is used to produce p-xylene selectively through toluene alkylation with methanol, xylene isomerization and toluene disproportionation (Figure 4.4). This is an example of a product selective reaction in which the reactant (toluene) is small enough to enter the pore but some of the initial products formed (o and w-xylene) are too large to diffuse rapidly out of the pore. /7-Xylene can, however. 

The pathways for the degradation of toluene and xylene under denitrifying and sulfate-reducing conditions have been studied most extensively, and they take place by reactions quite different from those used by aerobic bacteria. As an example, two anaerobes affiliated with known sulfate-reducing bacteria isolated from enrichments with crude oil were able to grow at the expense of a number of alkylated benzenes—strain oXySl with toluene, o-xylene, and o-ethyltoluene and strain mXySl with toluene, m-xylene, and m-ethyltoluene (Harms et al. 1999). 

It has become clear that benzoate occupies a central position in the anaerobic degradation of both phenols and alkylated arenes such as toluene and xylenes, and that carboxylation, hydroxylation, and reductive dehydroxylation are important reactions for phenols that are discussed in Part 4 of this chapter. The simplest examples include alkylated benzenes, products from the carboxylation of napthalene and phenanthrene (Zhang and Young 1997), the decarboxylation of o-, m-, and p-phthalate under denitrifying conditions (Nozawa and Maruyama 1988), and the metabolism of phenols and anilines by carboxylation. Further illustrative examples include the following ... 

A munber of organic compounds are suitable for use as tracers in a process for monitoring the flow of subterranean fluids. The following traces have been proposed benzene tetracarboxylic acid, methylbenzoic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, naphthalene-trisulfonic acid, alkyl benzene sulfonic acid, alkyl toluene sulfonic acid, alkyl xylene sulfonic acid, a-olefin sulfonic acid, salts of the foregoing acids, naphthalenediol, aniline, substituted aniline, pyridine, substituted pyridines [883]. 

Toluene alkylation with isopropyl alcohol was chosen as the test reaction as we can follow in a detail the effect of zeolite structural parameters on the toluene conversion, selectivity to cymenes, selectivity to para-cymene, and isopropyl/n-propyl ratio. It should be stressed that toluene/isopropyl alcohol molar ratio used in the feed was 9.6, which indicates the theoretical toluene conversion around 10.4 %. As you can see from Fig. 2 conversion of toluene over SSZ-33 after 15 min of T-O-S is 21 %, which is almost two times higher than the theoretical toluene conversion for alkylation reaction. The value of toluene conversion over SSZ-33 is influenced by a high rate of toluene disproportionation. About 50 % of toluene converted is transformed into benzene and xylenes. Toluene conversion over zeolites Beta and SSZ-35 is around 12 %, which is due to a much smaller contribution of toluene disproportionation to the overall toluene conversion. A slight increase in toluene conversion over ZSM-5 zeolite is connected with the fact that desorption and transport of products in toluene alkylation with isopropyl alcohol is the rate controlling step of this reaction [9]... 

The hydrogenation catalysts can be prepared in situ, starting from the surface alkyl complex. In terms of catalytic performances, these catalysts are highly effective (Table 6.21) [150]. The best hydrogenation systems are based on silica supported dinuclear complexes, for which the structures of the active sites have not been investigated. Hydrogenation of toluene and xylenes can be achieved under similar conditions. 

Other examples of systems that are likely to be governed by product shape selectivity effects include toluene disproportionation to para-xylene -i- benzene in favor of other xylenes r- benzene [61]. Toluene alkylation by methanol to give para-xylene in favor of other xylenes is yet another such example [76],... 

In the case of toluene alkylation with methanol an opportunity exists for para selectivity. Para-xylene ortho-xylene ratio was 3.1 over MFl and 0.6 over BEA framework types. 

In the past, several aluminum-alkyl, halide, and alkoxide complexes supported by multidentate ligands were examined for their catalytic lactide polymerization activities. To this end, monomeric aluminum complexes 148a, b (Fig. 21) were synthesized in our laboratory for producing polyesters with thiolate end groups [137]. These complexes initiated polymerizations under reflux condition in toluene and xylene forming PLAs with narrow molecular weight distributions (PDIs 1.15-1.25). 

Pig. 1 Scheme of main reaction routes of toluene alkylation by ethylene. (ET= ethyltoluene XYL=xylene S = selectivity to the product on converted toluene)... 

Aromatic compounds are typically no more than 15% of the total weight of most crude oil. The branched or alkylated aromatic derivatives are more prevalent than the nonalkylated aromatics. For example, toluene and xylene are found in higher percentages than benzene. Also, monoaromatic compounds such as toluene and xylene are some of the most common of the aromatics in crude. 

Fishbein, L. (1988) Genetic effects of benzene, toluene and xylene. In Fishbein. L. O Neill, I.K., eds. Environmental Carcinogens Methods of Analysis and Exposure Measurement. Vol. 10, Benzene and Alkylated Benzenes (lARC Scientific Publications No. 85). Lyon. lARC, pp. 19-46... 

Ipatieff and coworkers observed first that A1C13 catalyzes the destructive alkylation of aromatics with branched alkanes.179 For example, rm-butylbenzene (35%), p-di-rm-butylbenzene (25%), and considerable isobutane are the main products when benzene is reacted at 20-50°C with 2,2,4-trimethylpentane. Toluene and biphenyl are alkylated at 100°C in a similar way.180 Straight-chain alkanes required more severe reaction conditions. n-Pentane reacted at 175°C to yield 8% propylbenzene, 25% ethylbenzene, and 20% toluene.181 Phosphoric acid afforded similar products at higher temperature (450°C).182 Pentasil zeolites and dealumi-nated pentasils have been found to promote alkylation of benzene with C2—C4 alkanes to form toluene and xylenes.183,184... 

In a similar fashion, reductive alkylation of benzene, toluene, and xylenes with ben-zaldehyde, aromatic methyl ketones, and cycloalkanones can be induced by InCl3 in the presence of Me2SiClH 429... 

Friedel-Crafts alkylation of benzene,220 221 toluene,222para-xylene,220 and naphthalene223 with benzyl alcohols have been studied over Nafion-silica nano-composite catalysts, including the kinetics of alkylation.221,223 In most cases, 13% Nafion-silica showed the highest activity, testifying again to the much higher accessibility of the active sites. Complete conversion of para-xylene was found in the presence of triflic acid, and it was the only reaction when ether formation as side reaction did not occur. 

Activated arenes (toluene, meta-xylene, naphthalene) undergo acylation, whereas strongly deactivated arenes (nitrobenzene, acetophenone) do not react. On the basis of this information, the transformation was suggested to start with alkylation followed by the acylation step. 

Product distribution data (Table V) obtained in the hydrocracking of coal, coal oil, anthracene and phenanthrene over a physically mixed NIS-H-zeolon catalyst indicated similarities and differences between the products of coal and coal oil on the one hand and anthracene and phenanthrene on the other hand. There were differences in the conversions which varied in the order coal> anthracene>phenanthrene coal oil. The yield of alkylbenzenes also varied in the order anthracene >phenanthrene>coal oil >coal under the conditions used. The alkylbenzenes and C -C hydrocarbon products from anthracene were similar to the products of phenanthrene. The most predominant component of alkylbenzenes was toluene and xylenes were produced in very small quantities. Methane was the most and butanes the least predominant components of the gaseous product. The products of coal and coal oil were also found to be similar. The most predominant components of alkylbenzenes and gaseous product were benzene and propane respectively. The data also indicated distinct differences between products of coal origin and pure aromatic hydrocarbons. The alkyl-benzene products of coal and coal oil contained more benzene and xylenes and less toluene, ethylbenzene and higher benzenes when compared to the products from anthracene and phenanthrene. The gaseous products of coal and coal oil contained more propane and butanes and less methane and ethane when compared to the products of anthracene and phenanthrene. The differences in the hydrocracked products were obviously due to the differences in the nature of reactants. Coal and coal oil contain hydroaromatic, naphthenic, heterocyclic and aliphatic structures, in addition to polynuclear aromatic structures. Hydrocracking under severe conditions yielded more BTX as shown in Table VI. The yields of BTX obtained from coal, coal oil, anthracene and phenanthrene were respectively 18.5, 25.5, 36.0, and 32.5 percent. Benzene was the most... 

The converse reactions dealkylation and hydrodealkylation are practiced extensively to convert available feedstocks into other more desirable (marketable), products. Two such processes are (1) the conversion of toluene or xylene, or the higher-molecular-weight alkyl aromatic compounds, to benzene in the presence of hydrogen and a suitable presence of a dealkylation catalyst and (2) the conversion of toluene in the presence of hydrogen and a fixed bed catalyst to benzene plus mixed xylenes. 

Side-chain chlorinated alkyl aromatics based on toluene and xylene play an important role as chemical intermediates. They are used in the manufacture of a variety of chemical products including plastics, pharmaceuticals, flavors, pesticides, catalysts, and more. Monochlorination of the sidechain (Table 4, entry 37) is rather difficult. 

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