Extension of aromaticity

Group Branch Extension of Aromaticity Sigma/Rho Fragment Interaction Special ortho effects Crowding Intramolecular Hydrogen Bonding... 

Extension of aromaticity. The extension of the aromatic ring system through fusion (as in naphthalene) or direct substitution (as in biphenyl) appears to increase log P, especially if the heteroaromatic atom is next to the juncture. If the ring-joining carbons are attached only to other aromatic carbons, electron delocalization is minimal the correction is -rO.lO for each 1C. If the ICs are also attached... 

Of some significance is the extension of aromatic aldehydes into conjugated dien-als by reaction of a disilyl imine, and the generation of the (2-pyridylthio)methyl carbanion. ... 

Several studies have been carried out on the chain extension of aromatic polyesters through the use of various additive species over the last 20-30 years [162-190] many patents have also been applied for in this area [191-210]. 

The extension of aromatic systems by annulation reactions is an effective way of extending smaller PAHs into larger graphene-like structures [83]. In this context multiple approaches have been devised. 

Bis-2-oxazolines were described in the 1960s as useful in the preparation of poly(ester-amide)s and manufacturing processes were later developed, for instance, for chain extension of aromatic polyesters [68, 69]. Recently, bis-2-oxazolines have also been applied in the linking of LA based prepoly-... 

FIGURE 13.34 S ome simple extensions of aromaticity substituted, fused, and heterobenzene compounds, as well as a five-membered ring aromatic compound. 

Despite many controversial arguments regarding the definition and physical origin of aromaticity [1,15-17], the concept of aromaticity has crossed the boundary of benzenoid hydrocarbons [with (4n + 2)ji -electrons] to include heterosystems [50] like pyridine, thiophine, cations such as tropylium [12] and cyclopropenium [13], anions like cyclopentadienyl [51], organometallic systems, namely ferrocene [52], purely carbon-free systems [53,54], namely Pj, [(P5)2Ti]. The three-dimensional aromaticity of boron-based clusters [55] and of fullerenes [56], the homoaromaticity of cationic systems [57], aromaticity of triplet state annulenes [58], and pericyclic transition states [59] has enlarged the concept of aromaticity. Extension of aromaticity... 

Calculations for electrophilic substitution in the quinolinium ion can be compared with experiment, and for a range of values of h the predicted order of positional reactivities, s 8>6>3>7, agrees moderately well in a qualitative sense with the observed order of s 8>6>7>3 (table 10.3). Further evaluation of the method must await the results of more extensive calculations for a range of aromatic systems. 

The cross-coupling of aromatic and heteroaromatic rings has been carried out extensively[555]. Tin compounds of heterocycles such as oxazo-lines[556,557], thiophene[558,559], furans[558], pyridines[558], and seleno-phenes [560] can be coupled with aryl halides. The syntheses of the phenylo.xazoline 691[552], dithiophenopyridine 692[56l] and 3-(2-pyridyl)qui-noline 693[562] are typical examples. 

The rotating-disk contactor (RDC), developed in the Netherlands (158) in 1951, uses the shearing action of a rapidly rotating disk to interdisperse the phases (Eig. 15b). These contactors have been used widely throughout the world, particularly in the petrochemical industry for furfural [98-01-1] and SO2 extraction, propane deasphalting, sulfolane [126-33-0] extraction for separation of aromatics, and caprolactam (qv) [105-60-2] purification. Columns up to 4.27 m in diameter are in service. An extensive study (159) has provided an excellent theoretical framework for scale-up. A design manual has also been compiled (160). Detailed descriptions and design criteria for the RDC may also be found (161). 

TURBINE fuels), are both in demand. Solvent extraction is also extensively used to meet the growing demand for the high purity aromatics such as ben2ene, toluene, and xylene (BTX) as feedstocks for the petrochemical industry (see BTX PROCESSING FEEDSTOCKS,PETROCHEMICALS). Additionally, the separation of aromatics from aUphatics is one of the largest appHcations of solvent extraction (see Petroleum, refinery processes survey). 

A further consequence of association of acylating agents with basic compounds is an increase in the bulk of the reagent, and greater resistance to attack at the more stericaHy hindered positions of aromatic compounds. Thus acylation of chrysene and phenanthrene in nitrobenzene or in carbon disulfide occurs to a considerable extent in an outer ring, whereas acylation of naphthalene leads to extensive reaction at the less reactive but stericaky less hindered 2-position. 

Friedel-Crafts acylation using nittiles (other than HCN) and HCI is an extension of the Gattermann reaction, and is called the Houben-Hoesch reaction (120—122). These reactions give ketones and are usually appHcable to only activated aromatics, such as phenols and phenoHc ethers. The protonated nittile, ie, the nitrilium ion, acts as the electrophilic species in these reactions. Nonactivated ben2ene can also be acylated with the nittiles under superacidic conditions 95% trifluoromethanesulfonic acid containing 5% SbF (Hg > —18) (119). A dicationic diprotonated nittile intermediate was suggested for these reactions, based on the fact that the reactions do not proceed under less acidic conditions. The significance of dicationic superelectrophiles in Friedel-Crafts reactions has been discussed (123,124). 

Membrane modules have found extensive commercial appHcation in areas where medium purity hydrogen is required, as in ammonia purge streams (191). The first polymer membrane system was developed by Du Pont in the early 1970s. The membranes are typically made of aromatic polyaramide, polyimide, polysulfone, and cellulose acetate supported as spiral-wound hoUow-ftber modules (see Hollow-FIBERMEMBRANEs). 

Attempts have been made to develop methods for the production of aromatic isocyanates without the use of phosgene. None of these processes is currently in commercial use. Processes based on the reaction of carbon monoxide with aromatic nitro compounds have been examined extensively (23,27,76). The reductive carbonylation of 2,4-dinitrotoluene [121 -14-2] to toluene 2,4-diaLkylcarbamates is reported to occur in high yield at reaction temperatures of 140—180°C under 6900 kPa (1000 psi) of carbon monoxide. The resultant carbamate product distribution is noted to be a strong function of the alcohol used. Mitsui-Toatsu and Arco have disclosed a two-step reductive carbonylation process based on a cost effective selenium catalyst (22,23). 

Other Preparative Reactions. Polyamidation has been an active area of research for many years, and numerous methods have been developed for polyamide formation. The synthesis of polyamides has been extensively reviewed (54). In addition, many of the methods used to prepare simple amides are appHcable to polyamides (55,56). Polyamides of aromatic diamines and aUphatic diacids can also be made by the reaction of the corresponding aromatic diisocyanate and diacids (57). 

Styrene [100-42-5] (phenylethene, viaylben2ene, phenylethylene, styrol, cinnamene), CgH5CH=CH2, is the simplest and by far the most important member of a series of aromatic monomers. Also known commercially as styrene monomer (SM), styrene is produced in large quantities for polymerization. It is a versatile monomer extensively used for the manufacture of plastics, including crystalline polystyrene, mbber-modifted impact polystyrene, expandable polystyrene, acrylonitrile—butadiene—styrene copolymer (ABS), styrene—acrylonitrile resins (SAN), styrene—butadiene latex, styrene—butadiene mbber (qv) (SBR), and unsaturated polyester resins (see Acrylonithile polya rs Styrene plastics). 

The H NMR spectra of aromatic six-membered heterocycles have been measured extensively. The considerable amount of data which were available by 1972 were compiled by Batterham in an excellent critical monograph (B-73NMR), which provides the basis for the general account which follows here. 

NMR data for 4-methyloxazole have been compared with those of 4-methylthiazole the data clearly show that the ring protons in each are shielded. In a comprehensive study of a range of oxazoles. Brown and Ghosh also reported NMR data but based a discussion of resonance stabilization on pK and UV spectral data (69JCS(B)270). The weak basicity of oxazole (pX a 0.8) relative to 1-methylimidazole (pK 7.44) and thiazole (pK 2.44) demonstrates that delocalization of the oxygen lone pair, which would have a base-strengthening effect on the nitrogen atom, is not extensive. It must be concluded that not only the experimental measurement but also the very definition of aromaticity in the azole series is as yet poorly quantified. Nevertheless, its importance in the interpretation of reactivity is enormous. 

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. 

Certain highly porous solid materials selectively adsorb certain molecules. Examples are silica gel for separation of aromatics from other hydrocarbons, and activated charcoal for removing liquid components from gases. Adsorption is analogous to absorption, but the principles are different. Layers of adsorbed material, only a few molecules thick, are formed on the extensive interior area of the adsorbent - possibly as large as 50,000 sq. ft./lb of material. 

The term Birch reduction was originally applied to the reduction of aromatic compounds by alkali metals and an alcohol in ammonia. In recent years many chemists have used the term to include all metal-ammonia reductions, whether an alcoholic proton source is present or not. The author prefers to use the term Birch reduction to designate any reduction carried out in ammonia with a metal and a proton donor as or more acidic than an alcohol, since Birch customarily used such a proton donor in his extensive pioneering work. The term metal-ammonia reduction is best reserved for reductions in which ammonia is the only proton donor present. This distinction in terminology emphasizes the importance of the acidity of the proton donor in the reduction process. 

Fluorocylatwn of enarnines and enamides has been intensively studied by different groups [78, 79, 80 SI] The effectiveness of this particular electrophilic substitution reaction becomes obvious when the nitrogen atom of the enamine moiety is engaged in an aromatic system [82 S3] or when the olefinic system is part of an aromatic nucleus [84] (equations 37 and 38) A further extension of this reaction is demonstrated by the tnfluoracetylation of aldehyde dialkyl hydrazones [S5 86] (equation 39)... 

Extensions of the enamine alkylation to a-tetralones have also been used (245-248), but product yields were lower, presumably due to steric crowding in a transition state where generation of an imonium salt gives rise to a repulsion between a methylene group on nitrogen and a peri aromatic proton. 

Extensions of 1,3-dipolar additions of aromatic azides (720,721) to other enamines (636), and particularly to the enamine tautomer of SchilTs bases, were explored (722,723). Further nitrone additions were reported (724,725) and a double nitrile oxide added to an endiamine (647). Cyanogen azide and enamines gave cyanoamidines through rearrangement (726). 

Attenlion should be drawn to ihe use of tin oxide systems as heterogeneous catalysts. The oldest and mosi extensively patented systems are the mixed lin-vanadium oxide catalysis for the oxidation of aromatic compounds such as benzene, toluene, xylenes and naphthalene in the. synthesis of organic acids and acid anhydride.s. More recenily mixed lin-aniimony oxides have been applied lo the selective oxidaiion and ammoxidaiion of propylene to acrolein, acrylic acid and acrylonilrile. 

Rapid double-bond shifts, extensive skeletal isomerization, H-transfer is major and selective for tertiary olefins large amounts of aromatics formed from aliphatics at 932°F (50t) O... 

Five-membered heteroaromatic ring compounds have been extensively studied in terms of their relative reactivity and specific physicochemical properties. In particular, it is generally accepted that the degree of aromaticity follows the order... 

In a more recent paper (Stovpovoi et al., 1991b) Bagal and coworkers interpret their observation that Arrhenius plots of the rates of various N- and C-couplings of aromatic amines (e. g., 1-naphthylamine, 2,6-naphthylaminesulfonic acid, and 4-me-thylaniline) are linear only in aqueous systems, but not in aprotic solvents such as nitromethane or acetonitrile. Their explanation is based on an extension of the clas-... 

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