Hydrocarbons, aromatic, alkylation table

A comparative analysis of the kinetics of the reactions of atoms and radicals with paraffinic (R1 ), olefinic (R2H), and aromatic alkyl-substituted (R3H) hydrocarbons within the framework of the parabolic model permitted a new important conclusion. It was found that the tt-C—C bond occupying the a-position relative to the attacked C—H bond increases the activation energy for thermally neutral reaction [11]. The corresponding results are presented in Table 6.9. 

Figure 6.8 Relationship of enthalpy to log k values. Column, ODS silica, ERC-ODS, 15 cm x 6.0 mm i.d. eluent, 80% aqueous acetonitrile at 30 °C. Numbers beside symbols see Table 6.4. O, Polycyclic aromatic hydrocarbons x, alkyl-benzenes, O, halogenated benzenes A, alkanols and , alkanes.

Further analyses of representative extracts of each of the Amberlite resins employing GC-MS indicated the presence of significant concentrations of a variety of aromatic hydrocarbons, including alkylated derivatives of benzene, styrene, naphthalene, and biphenyl. A more comprehensive listing of these contaminants, including their approximate concentrations in the sorbent matrix, is provided in Table I. 

Satisfactory results were obtained in the Nafion-H-catalyzed gas-phase alkylation of aromatic hydrocarbons with alkyl halides235 [Eq. (5.88)]. Alkylhalides are reactive Friedel-Crafts alkylating agents and give high conversions when alkylating benzene in the gas phase over Nafion-H catalyst. For example, in the alkylation of benzene with isopropyl chloride, conversions as high as 87% were achieved (Table 5.17, run 11). Conversions, however, were temperature and contact time dependent (Table 5.17). 

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... 

This procedure illustrates a general method for preparing aromatic hydrocarbons by the tandem alkylation-reduction of aromatic ketones and aldehydes.2 Additional examples are given in Table I. 

More than 25 different substituted urea herbicides are currently commercially available [30, 173]. The most important are phenylureas and Cycluron, which has the aromatic nucleus replaced by a saturated hydrocarbon moiety. Benzthiazuron and Methabenzthiazuron are more recent selective herbiddes of the class, with the aromatic moiety replaced by a heterocyclic ring system. With the exception of Fenuron, substituted ureas (i.e., Diuron, Fluometuron, Fig. 10, Table 3) exhibit low water solubilities, which decrease with increasing molecular volume of the compound. The majority of the phenylureas have relatively low vapor pressures and are, therefore, not very volatile. These compounds show electron-donor properties and thus they are able to form charge transfer complexes by interaction with suitable electron acceptor molecules. Hydrolysis, acylation, and alkylation reactions are also possible with these compounds. 

Example 2 Separation of a polycyclic aromatic hydrocarbon and an alkyl benzoate. The logP values of fluorene and butyl benzoate are 3.91 and 3.74, respectively, from Table 4.1. The separation is poor in 50% aqueous aceto-... 

Representative couplings of aromatic hydrocarbons are summarized in Table 10. Alkyl-substituted aromatic hydrocarbons can be coupled to diphenyls and/or diphenylmethanes depending on their substitution pattern (Table 10, numbers 1-6). Reactions occur according to Scheme 9, paths (a) and (c). 

With stringent precautions to avoid the presence of water, polycyclic aromatic hydrocarbons show two one-electron reversible waves on cyclic voltammetry in dimethylformamide (Table 7.1). These are due to sequential one-electron additions to the lowest unoccupied molecular n-orbital [1]. Hydrocarbons with a single benzene ring are reduced at very negative potentials outside the accessible range in this solvent. Radical-anions of polycyclic aromatic hydrocarbons [2] and also alkyl benzenes [3] were first obtained by the action of alkali metals on a solution of the hydrocarbon in tetrahydrofuran. They have been well characterised by esr spectroscopy. The radical-anions form coloured solutions with absorption bands at longer wavelength than the parent hydrocarbon [4,5]. 

Table XII presents compositional data for the aromatic hydrocarbons present in the anthracene oil. Compounds in the -12(H), -14(H), -18(H), and -22(H) series account for 78% of the aromatic hydrocarbons. The -12(H) compounds identified by GC/MS include naphthalene, 1- and 2-methylnaphthalene and at least 5 naphthalenes possessing 2 alkyl carbons. By GC/MS, acenaphthene and biphenyl account for 94% and 6%, respectively, of the first homolog in the -14(H) series. The parent member of the -18(H) series (C2.4H10 waS PreParat -ve -y isolated using GC and identified by UV and NMR to be >98% phenanthrene. The dominance of phenanthrene over anthracene in both high- and low- temperature coal tars has been previously noted (29,30,40,41,42,43). Thus, phenanthrene and presumably its alkylated homologs comprise the -18(H) Z series and account for 15.4% of the anthracene oil. The initial homolog in the -22(H) series, is comprised of 58%...

Gas chromatography has been applied to the determination of a wide range of organic compounds in trade effluents including the following types of compounds which are reviewed in Table 15.15 aromatic hydrocarbons, carboxylic acids aldehydes, non ionic surfactants (alkyl ethoxylated type) phenols monosaccharides chlorinated aliphatics and haloforms polychlorobiphenyls chlorlignosulphonates aliphatic and aromatic amines benzidine chloroanilines chloronitroanilines nitrocompounds nitrosamines dimethylformamide diethanolamine nitriloacetic acid pyridine pyridazinones substituted pyrrolidones alkyl hydantoins alkyl sulphides dialkyl suphides dithiocaibamate insecticides triazine herbicides and miscellaneous organic compounds. 

Such polycyclic aromatic hydrocarbons as anthracene or heteroaromatics as acridine, phenazine and 2,4,5-triphenyl oxazole act as Jt-donors for the Jt-acceptors AN and alkyl methacrylates [50-53]. Again, the interaction of the donor excited states with vinyl monomers leads to exciplex formation. But, the rate constants (k ) of these quenching processess are low compared to other quenching reactions (see Table 1). The assumed electron transfer character is supported by the influence of the donor reduction potential on the k value (see Table 1), and the detection of the monomer cation radicals with the anthracene-MMA system. Then, the ion radicals initiate the polymerization, the detailed mechanism of which is unsolved,... 

Oxidation of hydrocarbons with dioxygen is more facile when the C-H bond is activated through aromatic or vinylic groups adjacent to it. The homolytic C-H bond dissociation energy decreases from ca. 100 kcal mol-1 (alkyl C-H) to ca. 85 kcal mol-1 (allylic and benzylic C-H), which makes a number of autoxidation processes feasible. The relative oxidizability is further increased by the presence of alkyl substituents on the benzylic carbon (see Table 4.6). The autoxidation of isopropylbenzene (Hock process, Fig. 4.49) accounts for the majority of the world production of phenol [131] ... 

Trimethylsilyl anions also give the substitution products by the reaction with alkyl chloride in almost quantitative yield (equation 14), but considerable amounts of electron-transfer products are produced as well in HMPA. Indeed, Mc3SiNa/HMPA is an excellent reagent to produce anion radicals (Table 9) from aromatic hydrocarbons for ESR (electron spin resonance) studies (equation 65). ... 

Representative couplings of aromatic hydrocarbons are summarized in Table 1. Alkyl-substituted aromatic hydrocarbons can be coupled to diphenyls and/or diphenylmethanes depending on their substitution pattern (Table 1, numbers 1-6). The initially formed radical cation I [Eq. (3)] reacts with the starting compound to the diphenyl (II) (Eq. (3), path a] or loses a proton to form a benzyl radical [Eq. (3), path b], which after oxidation to the cation undergoes an electrophilic aromatic substitution at the starting compound to form the diphenylmethane (III). A low charge density on an unsubstituted carbon atom of I favors path a, whereas a low charge density on a substituted carbon atom favors path b[4]. 

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