Aromatic compounds, separation

HMO theory is named after its developer, Erich Huckel (1896-1980), who published his theory in 1930 [9] partly in order to explain the unusual stability of benzene and other aromatic compounds. Given that digital computers had not yet been invented and that all Hiickel s calculations had to be done by hand, HMO theory necessarily includes many approximations. The first is that only the jr-molecular orbitals of the molecule are considered. This implies that the entire molecular structure is planar (because then a plane of symmetry separates the r-orbitals, which are antisymmetric with respect to this plane, from all others). It also means that only one atomic orbital must be considered for each atom in the r-system (the p-orbital that is antisymmetric with respect to the plane of the molecule) and none at all for atoms (such as hydrogen) that are not involved in the r-system. Huckel then used the technique known as linear combination of atomic orbitals (LCAO) to build these atomic orbitals up into molecular orbitals. This is illustrated in Figure 7-18 for ethylene. 

Hydrogenation of the aromatic ring to form naphthenic compounds has been proposed as a route to faciUtate the separation of the Cg aromatic isomers (31). The spread in boiling points of the naphthenic compounds is 12°C vs a spread of 8°C for the aromatic compounds. However, the cycloparaffinic products obtained from OX and EB boil only 3°C apart, impeding the separation. 

Werner complexes can be used to form clathrates with the Cg aromatic isomers (35—42). The aromatic compounds are released upon heating. Since the uptake and release characteristics of the four Cg aromatic isomers are each different, this method has been suggested as a means of separating the isomers. 

Inclusion compounds of the Cg aromatic compounds with tris((9-phenylenedioxy)cyclotriphosphazene have been used to separate the individual isomers (43—47). The Schardinger dextrins, such as alpha-cyclodextrin, beta-dextrin, and gamma-dextrin are used for clathration alpha-dextrin is particularly useful for recovering PX from a Cg aromatic mixture (48,49). PyromeUitic dianhydride (50) and beryllium oxybenzoate (51) also form complexes, and procedures for separations were developed. 

A schematic of the MGCC process is shown in Figure 9. The mixed Cg aromatic feed is sent to an extractor (unit A) where it is in contact with HF—BF and hexane. The MX—HF—BF complex is sent to the decomposer (unit B) or the isomerization section (unit D). In the decomposer, BF is stripped and taken overhead from a condensor—separator (unit C), whereas HF in hexane is recycled from the bottom of C. Recovered MX is sent to column E for further purification. The remaining Cg aromatic compounds and hexane are sent to raffinate column E where residual BE and HE are separated, as well as hexane for recycle. Higher boiling materials are rejected in column H, and EB and OX are recovered in columns I and J. The overhead from J is fed to unit K for PX separation. The raffinate or mother Hquor is then recycled for isomerization. 

Bentone-34 has commonly been used in packed columns (138—139). The retention indices of many benzene homologues on squalane have been determined (140). Gas chromatography of C —aromatic compounds using a Ucon B550X-coated capillary column is discussed in Reference 141. A variety of other separation media have also been used, including phthaUc acids (142), Hquid crystals (143), and Werner complexes (144). Gel permeation chromatography of alkylbenzenes and the separation of the Cg aromatics treated with zeofltes ate described in References 145—148. 

Silver fluorocomplexes are also used ia the separation of olefin—paraffin mixtures (33), nitration (qv) of aromatic compounds (34), ia the synthesis of (9-bridged bicycHcs (35), pyrroles (36), cyclo-addition of vinylbromides to olefins (37), and ia the generation of thioben2oyl cations (38). 

Methyl- and dimethylnaphthalenes are contained in coke-oven tar and in certain petroleum fractions in significant amounts. A typical high temperature coke-oven coal tar, for example, contains ca 3 wt % of combined methyl- and dimethylnaphthalenes (6). In the United States, separation of individual isomers is seldom attempted instead a methylnaphtha1 ene-rich fraction is produced for commercial purposes. Such mixtures are used for solvents for pesticides, sulfur, and various aromatic compounds. They also can be used as low freezing, stable heat-transfer fluids. Mixtures that are rich in monomethyinaphthalene content have been used as dye carriers (qv) for color intensification in the dyeing of synthetic fibers, eg, polyester. They also are used as the feedstock to make naphthalene in dealkylation processes. PhthaUc anhydride also can be made from m ethyl n aph th al en e mixtures by an oxidation process that is similar to that used for naphthalene. 

Process Stream Separations. Differences in adsorptivity between gases provides a means for separating components in industrial process gas streams. Activated carbon in fixed beds has been used to separate aromatic compounds from lighter vapors in petroleum refining process streams (105) and to recover gasoline components from natural and manufactured gas (106,107). 

New stationary phases for specific purposes in chromatographic separation are being continually proposed. Charge transfer adsorption chromatography makes use of a stationary phase which contains immobilised aromatic compounds and permits the separation of aromatic compounds by virtue of the ability to form charge transfer complexes (sometimes coloured) with the stationary phase. The separation is caused by the differences in stability of these complexes (Porath and Dahlgren-Caldwell J Chromatogr 133 180 1977). 

In general, the dissection of substituertt effects need not be limited to resonance and polar components, vdiich are of special prominence in reactions of aromatic compounds.. ny type of substituent interaction with a reaction center could be characterized by a substituent constant characteristic of the particular type of interaction and a reaction parameter indicating the sensitivity of the reaction series to that particular type of interactioa For example, it has been suggested that electronegativity and polarizability can be treated as substituent effects separate from polar and resonance effects. This gives rise to the equation... 

Superfractionation is an extension of distillation using smaller diameter columns and 100 or more trays to achieve reflux ratios exceeding 5 1. This equipment separates a narrow range aunponents such as of high-purity solvents, e.g., isoparaffins or individual aromatic compounds foi use. IS petrochemicals. 

Wines and other alcoholic beverages such as distillates represent very complex mixtures of aromatic compounds in an ethanol-water mixture. Once an extract or concentrate of the required compounds is prepared, a suitable chromatographic system must be used to allow separation and resolution of the species of interest. Many applications have been developed that use MDGC. 

One example of normal-phase liquid chromatography coupled to gas chromatography is the determination of alkylated, oxygenated and nitrated polycyclic aromatic compounds (PACs) in urban air particulate extracts (97). Since such extracts are very complex, LC-GC is the best possible separation technique. A quartz microfibre filter retains the particulate material and supercritical fluid extraction (SPE) with CO2 and a toluene modifier extracts the organic components from the dust particles. The final extract is then dissolved in -hexane and analysed by NPLC. The transfer at 100 p.1 min of different fractions to the GC system by an on-column interface enabled many PACs to be detected by an ion-trap detector. A flame ionization detector (PID) and a 350 p.1 loop interface was used to quantify the identified compounds. The experimental conditions employed are shown in Table 13.2. 

Figure 13.16 LC separation of urban air particulate exrtact (a), along with the GC/FID cliro-matogram (b) of an oxy-PAC fraction (transfeired via a loop-type interface). Reprinted from Environmental Science and Technology, 29, A. C. Lewis et al., On-line coupled LC-GC-ITD/MS for the identification of alkylated, oxygenated and nirtated polycyclic aromatic compounds in urban air particulate exti acts , pp. 1977-1981, copyright 1995, with permission from the American Chemical Society.

Friedel-Crafts acylation reactions usually involve the interaction of an aromatic compound with an acyl halide or anhydride in the presence of a catalyst, to form a carbon-carbon bond [74, 75]. As the product of an acylation reaction is less reactive than its starting material, monoacylation usually occurs. The catalyst in the reaction is not a true catalyst, as it is often (but not always) required in stoichiometric quantities. For Friedel-Crafts acylation reactions in chloroaluminate(III) ionic liquids or molten salts, the ketone product of an acylation reaction forms a strong complex with the ionic liquid, and separation of the product from the ionic liquid can be extremely difficult. The products are usually isolated by quenching the ionic liquid in water. Current research is moving towards finding genuine catalysts for this reaction, some of which are described in this section. 

Starting with benzene as your only7 source of aromatic compounds, how would you synthesize the following substances Assume that you can separate ortho and para isomers if necessary. 

A number of radical anions of sulfur-containing aromatic compounds have been studied essentially by means of ESR spectroscopy and sometimes by electronic spectroscopy. The studied compounds include aromatic rings separated by the oxidized sulfur functionality. The effects caused by the latter depend on the geometry and topology of the aromatic systems as well as on the electron-withdrawing ability of the other substituents. 

Ferrocene behaves in many respects like an aromatic electron-rich organic compound which is activated toward electrophilic reactions.In Friedel-Crafts type acylation of aromatic compounds with acyl halides, ferrocene is lO times more reactive than benzene and gives yields over 80%. However, ferrocene is different from benzene in respect to reactivity and yields in the Friedel-Crafts alkylation with alkyl halides or olefins. The yields of ferrocene alkylation are often very low. and the separations of the polysubstituted byproducts are tedious. 

Coman et al. [82] used a new modeling of the chromatographic separation process of some polar (hydroxy benzo[a]pyrene derivatives) and nonpolar (benzo[a]pyrene, dibenz[a,/ ]anthracene, and chrysene) polycyclic aromatic compounds in the form of third-degree functions. For the selection of the optimum composition of the benzene-acetone-water mobile phase used in the separation of eight polycyclic aromatic compounds on RP-TLC layers, some computer programs in the GW-BASIC language were written. 

Depending on activation and development conditions, the Rj values of three main separated fractions may change but their ranges are approximately as follows 0.40 to 1.00 (aliphatic hydrocarbons), 0.05 to 0.40 (aromatic compounds), and 0.00 to 0.05 (polar compounds fractions) [49,72,76]. 

Wise SA, Chesisr SN, Hertz HS, Hilpert LR, and May WE (1977) A chemically bonded amino-silane stationary phase for the high-performance liquid chromatographic separation of polynuclear aromatic compounds. Anal Chem 49 2306-2310. 

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