Aromatic compounds interesting/important

Compounds of special interest whose preparation is described include 1,2,3-benzothiadiazole 1,1-dioxide (a benzyne precursor under exceptionally mild conditions), bis(l,3-diphenylimida-zolidinylidene-2) (whose chemistry is quite remarkable), 6- di-melhylamino)julvene (a useful intermediate for fused-ring non-benzenoid aromatic compounds), dipkenylcyclopropenone (the synthesis of which is a milestone in theoretical organic chemistry), ketene di(2-melhoxyethyl) acetal (the easiest ketene acetal to prepare), 2-methylcyclopenlane-l,3-dione (a useful intermediate in steroid synthesis), and 2-phenyl-5-oxazolone (an important intermediate in amino acid chemistry). 

Acylation of aromatic compounds (Friedel-Crafts (FC) acylation), of great industrial interest, suffers from an important catalysis problem [69]. Most of the Lewis acids used as catalysts (traditionally metal chlorides such as A1C13) complex preferentially... 

Among complexes of organic compounds with N-centered electrophiles, a special position is occupied by the nitrosonium complexes. Interest in these complexes has not diminished over the years as they are intermediates in several important organic reactions, such as nitrosation of aromatic compounds (35),... 

The commercially most interesting metal complex pigments within the azo series are those obtained from aromatic o,o -dihydroxyazo compounds, while important products within the azomethine series are nickel or copper complexes of aromatic o,o -dihydroxyazomethine compounds. 

There is interest in applying genetic engineering to increase the output of the shikimate pathway for production of industrially important aromatic compounds, e.g., the dye indigo, which is used in manufacture of blue denim (Box 25-C). Study of the enzymes involved has led to the development of potent inhibitors of the shikimate pathway which serve as widely used herbicides.2 3... 

Electroenzymatic reactions are not only important in the development of ampero-metric biosensors. They can also be very valuable for organic synthesis. The enantio- and diasteroselectivity of the redox enzymes can be used effectively for the synthesis of enantiomerically pure compounds, as, for example, in the enantioselective reduction of prochiral carbonyl compounds, or in the enantio-selective, distereoselective, or enantiomer differentiating oxidation of chiral, achiral, or mes< -polyols. The introduction of hydroxy groups into aliphatic and aromatic compounds can be just as interesting. In addition, the regioselectivity of the oxidation of a certain hydroxy function in a polyol by an enzymatic oxidation can be extremely valuable, thus avoiding a sometimes complicated protection-deprotection strategy. 

The Dess-Martin periodinane 8 is also able to oxidize aromatic compounds to the corresponding quinones. The presence of water is important and, starting from anilides 42 substituted in the 2-position, the rare class of ortho-imido-quinones 43 is accessible, Scheme 21. It has been shown that compounds of type 43 are interesting building blocks and can lead to polycyclic molecules of diverse molecular architecture [95,96]. They can undergo subsequent Diels-Alder reactions and intramolecular versions have been used for a rapid access to natural products and for synthesis of scaffolds for further manipulation.para-Quinones 45 are also easily accessible, however, only in modest yields by reacting 4-sub-stituted anilines 44 under the same reaction conditions, Scheme 21 [97]. 

The observed electrophilic reactivity is indicative of superelectrophilic activation in the dication 173. Other ammonium-carboxonium dications have also been reported in the literature, some of which have been shown to react with benzene or other weak nucleophiles (Table 4).1 42b 57-60 Besides ammonium-carboxonium dications (175-179), a variety of N-heteroaromatic systems (180-185) have been reported. Several of the dicationic species have been directly observed by low-temperature NMR, including 176, 178-180, 183, and 185. Both acidic (175, 180-185) and non-acidic carboxonium (176-177) dicationic systems have been shown to possess superelectrophilic reactivity. The quinonemethide-type dication (178) arises from the important biomolecule adrenaline upon reaction in superacid (entry 4). The failure of dication 178 to react with aromatic compounds (like benzene) suggests only a modest amount of superelectrophilic activation. An interesting study was done with aminobutyric acid... 

The role of aromatic photonitration and photonitrosation processes in natural waters is still not clearly understood. It is, however, very interesting to report that nitration and nitrosation of monolinuron have been observed upon photolysis of nitrate and nitrite at environmental concentration levels [144], Studies on the environmental importance of such reactions will indeed benefit from the use of HPLC-MS-MS techniques for both process studies and field analysis, as they allow much lower detection limits to be reached when compared with traditional HPLC techniques. In the case of process studies, it would be very interesting to determine the extent at which the pathways observed for the photonitration and photonitrosation of aromatic compounds at fairly high concentration levels can be extrapolated to environmental conditions. 

Compounds of the type Cp2MX3 are also very important and the hydrides are particularly interesting 78 they catalyze the exchange of D2 with aromatic compounds at 1 to 2 atm and 80 to 100°C. The pentahydride, TaH5(diphos)2, will also do this. The mechanism involves dissociation to form the mono-hydrido species and oxidative addition of benzene, namely,... 

The key papers in this regard are those of Oren and coworkers [642-646], in which the importance of the pHra is emphasized. They were discussed in Section III.B. Representative results of Cohen et al. [645] are summarized in Table 18. Of special interest here is the coupling of adsorption, especially of polar aromatic compounds, with the electrochemical reactions on (electro)chemically modified carbon surfaces. This issue has since been considered by many investigators [647-632,493,653-669]. However, the factors governing the propensity for and the extent of adsorption have not been discussed in much detail, except to make the (often vaguely stated) point that the solution pH and the nature of the carbon surface are important. The studies of Vasquez et al. [650] and Woodard et al. [493] have gone farthest in this direction they are discussed in more detail in Section VI, The investigations summarized below serve to illustrate both the... 

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