Benzenes, monosubstituted, selective

To define the effectiveness of the UV/H202 process on a wide range of priority pollutants in water, Sundstrom et al. (1989) conducted experiments in a recirculating flow reactor system with low-pressure UV lamps at 254 nm. The temperature of the solution was maintained at 25°C, and pH was maintained at 6.8 by a phosphate buffer. Molar ratio of peroxide to pollutant was varied during the experiments. As the molar ratio of peroxide to pollutant increased, the reaction rates increased. Three monosubstituted benzenes were selected to examine the effect of a single substituent group on the rate of reaction of benzene. The rates of reaction were of similar magnitude for benzene and monosubstituted benzenes (toluene, chlorobenzene, and phenol) at the ratio of 7 for peroxide to pollutant. 

If, on the other hand, the encounter pair were an oriented structure, positional selectivity could be retained for a different reason and in a different quantitative sense. Thus, a monosubstituted benzene derivative in which the substituent was sufficiently powerfully activating would react with the electrophile to give three different encounter pairs two of these would more readily proceed to the substitution products than to the starting materials, whilst the third might more readily break up than go to products. In the limit the first two would be giving substitution at the encounter rate and, in the absence of steric effects, products in the statistical ratio whilst the third would not. If we consider particular cases, there is nothing in the rather inadequate data available to discourage the view that, for example, in the cases of toluene or phenol, which in sulphuric acid are nitrated at or near the encounter rate, the... 

Table 6 lists proton chemical shifts for a selection of monosubstituted furans including some with a metal or other less common heteroatom attached to the ring, but perhaps it should be noted that values are not closely comparable unless obtained in closely comparable conditions. Solvents can have a substantial effect upon chemical shifts (66CR(B)(263)1227>, especially benzene (72JA8854). Table 7 lists some ring interproton coupling constants and Table 8 some shift values for disubstituted furans. Polysubstituted furans are covered in the reviews and compilations mentioned above. 

Carbon-13 shift values of a small selection of monosubstituted benzenes [383] are collected in Table 4.53. Signal assignments are based on conventional techniques such as proton off-resonance and gated decoupling as well as comparative measurements of specifically deuterated compounds [384],... 

Table 1 ortho para Selectivities in chlorination of monosubstituted benzenes with TBH -zeolite HNaX in acetonitrile... 

Thiolate anions37 38 and oxime alkoxides38 react under phase transfer conditions to give aryl sulfides and O-aryl oximes, respectively the o-dichloro benzene complex can be converted selectively to the monosubstitution product (equation 9). The arylation of oximes leads to a simple process for benzofuran formation (equation 10). Simple primary and secondary amine nucleophiles react smoothly in the absence of added base, in a very general and efficient process for aniline derivatives.49... 

The additivity treatment also allows one to evaluate the influence of substituents which are otherwise obtainable only with difficulty. The study of the non-catalytic bromination of the halo-substituted poly-methylbenzenes by Illuminati and Marino (1956) allowed the evaluation of the partial rate factors for the highly deactivating m- and p-halogens. These data for the slow, highly selective bromination are inaccessible by other techniques. Analysis of the relative rates is made by application of the additivity equations (5) and (6) as described in Section I. An important aspect of the chemistry of the substituted polymethyl-benzenes, in contrast to the monosubstituted benzenes, is the large difference in p for bromination. The partial rate factors derived for each reaction are correlated with good precision by the tr4 -constants (Figs. 11 and 19). Yet the susceptibility of the reactions to the influence of substituents is altered by more than 25%. As already noted, this aspect of the problem is not well defined and is worthy of additional attention. 

The observations for the electrophilic substitution reactions of the monosubstituted benzenes have been examined for adherence to a linear free-energy relationship. As shown, the Selectivity Relationship,... 

Coulombic forces will determine the regioselectivity of the ortho addition [189], In the charge-transfer complexes of monosubstituted benzenes with alkenes, the charge (positive or negative) on the arene is largely located at the carbon atoms ipso and (to a lesser extent) para to the substituent. The carbon atoms of the alkene double bond will preferentially be located in the neighborhood of either the ipso carbon or (to a lesser extent) the para carbon atom of the monosubstituted benzene. This would explain the 1,2 and 3,4 selectivity in the ortho photocycloaddition. 

The partial rate factors vary within wide limits. Electrophilic species of lower activity, such as molecular bromine, are more selective, i.e., more capable of discriminating either between thiophene and benzene or between positions a and j8 of thiophene. Quantitatively, a linear trend is observed (Fig. 1) between loga/j3 and logotf. This is a correlation formally analogous to the selectivity relationship proposed by Brown and Nelson188 for the reactions of monosubstituted benzenes. 

Nitration of monosubstituted aromatics, toluene in particular, has been extensively studied using zeolites in order to direct the reaction towards the formation of the desired para-isomer. Toluene has been nitrated para-selectively with benzoyl nitrate over zeolite catalysts.[14,15] For example, when mordenite is used as a catalyst, MNTs are formed in almost quantitative yields, giving 67 % of the para-isomer in 10 min, but tetrachloromethane is required as solvent. However, the main problems associated with the use of benzoyl nitrate are handling difficulties due to its sensitivity toward decomposition, and the tendency toward detonation upon contact with rough surfaces. Nagy et a/.[19 21] reported the nitration of benzene, chlorobenzene, toluene and o-xylene with benzoyl nitrate in the presence of an amorphous aluminosilicate, as well as with zeolites HY and ZSM-11, in hexane as a... 

Using Menke s conditions, Smith et al.[29,30] have described a method for the nitration of benzene, alkylbenzenes and halogenobenzenes using zeolites with different topologies (HBeta, HY, HZSM-5 and HMordenite) as catalysts and a stoichiometric amount of nitric acid and acetic anhydride. The reactions were carried out without solvent at temperatures between -50 °C and 20 °C. For the nitration of toluene, tridirectional zeolites HBeta and HY were the most active catalysts achieving >99 % conversion in 5 min reaction time. However, HY exhibited selectivity to the p-nitrotoluene very similar to the homogeneous phase, while with HBeta, selectivities to p-nitrotoluene higher than 70% could be achieved. HBeta zeolite exhibited excellent para-selectivity for the nitration of the different monosubstituted aromatics (Table 5.1). The catalyst can be recycled and the only by-product, acetic acid, can be separated by vacuum distillation. 

Gomberg-Bachmann biphenyl synthesis. Reaction of stable arenediazonium tet-rafluoroborates or hexafluorophosphates in an aromatic solvent with potassium acetate (2 equiv.) and a phase-transfer catalyst results in biar Is in high yield. Crown ethers, Aliquat 336, and tetrabutylammonium hydrogen sulfate arc all effective catalysts. The reaction is useful for synthesis of unsymmetrical biaryls. The ortho-isomer predominates in reactions with a monosubstituted benzene. The most selective method is to couple a substituted arenediazonium salt with a symmetrical arene. 

The isomer distribution for anodic acetoxylation of a number of monosubstituted benzenes has been determined [122]. The reaction closely resembles ordinary electrophilic aromatic substitution processes, perhaps on the side of low-selectivity reactions. The isotope effect, A h//cd, for nuclear acetoxylation in anisole was found to be 1.0, whereas for a-substitution in ethylbenzene a value of 2.6 was observed. The interpretation of these values is not straightforward [126]. 

The pioneering work of a coupling of aromatic and heteroaromatic compounds with acetylenes was reported by Yamazaki et al. in 1979 [35]. Reaction of benzene with diphenylacetylene gives triphenylethene in 45% yield. In the case of the monosubstituted benzene, the reaction of toluene proceeds at the meta position selectively but the reaction of anisol takes place at the ortho position (Eq. 21). They proposed that the site-selectivity stems from an inductive effect of an elec-... 

Gao, X., Davies, J.P., and Weaver, M.J. (1990) A test of surface selection rules for surface-enhanced Raman scattering the orientation of adsorbed benzene and monosubstituted benzenes on gold. Journal of Physical Chemistrv, 94, 6858-6864. 

All monosubstituted benzenes react with the same regio- and enantio-selectivity whether the substituent is halogen, alkyl, alkenyl, C02H, CN, COMe, OMe or CF3. Thus toluene gives the diol 76 that can be produced at 3g/litre in the broth described above. It is also a commercial product. 

---