Cations, reactivity towards benzene

The general discussion (Section 4.02.1.4.1) on reactivity and orientation in azoles should be consulted as some of the conclusions reported therein are germane to this discussion. Pyrazole is less reactive towards electrophiles than pyrrole. As a neutral molecule it reacts as readily as benzene and, as an anion, as readily as phenol (diazo coupling, nitrosation, etc.). Pyrazole cations, formed in strong acidic media, show a pronounced deactivation (nitration, sulfonation, Friedel-Crafts reactions, etc.). For the same reasons quaternary pyrazolium salts normally do not react with electrophiles. 

The obtained l3C and 29Si NMR data do not vary significantly with the solvent as long as aromatic hydrocarbons are used. That is the maximum solvent effect on l3C NMR chemical shift, AS l3C w/v, for cation 9a is AS I3C w/v = 0.5 when the solvent is changed from benzene to toluene and the position of the 29Si resonance remains even unchanged. This indicates negligible interaction between the cation and solvent molecules, in particular no Wheland-type intermediates are formed. (38) Solvents other than aromatic hydrocarbons are however reactive towards vinyl cations 8-10 (see below). 

In all cases, superelectorophilic dicationic intermediates3 5 were suggested to be involved in the activation of carbonyl compounds based on the observation that protonated /V-heterocycles significantly enhance the reactivity of adjacent carbo-cationic centers. For example, cyclohexanone and acetophenone are unreactive toward benzene in triflic acid, whereas 4-piperidones252 and acetylpyridines254 react readily. Likewise, 3-pyridinecarboxaldehyde is able to alkylate deactivated... 

It is well known that electron-donating groups attached to benzene greatly enhance the ring s reactivity towards electrophilic substitution reactions, whereas electron-attracting groups decrease such reactivity markedly. Like most aromatic systems, ferrocene undergoes electrophilic substitution reactions readily. Care must be exercised because of the ease of oxidation of ferrocene to the ferricinium cation. Thus ferrocene cannot be nitrated, chlorinated, or brominated. Acetylation under a variety of conditions (63) has been successful, however. Under intensive Friedel-Crafts conditions further acetylation of acetylferrocene took place exclusively... 

Most of the olefin complexes examined in this study exhibit an unspectacular reactivity towards molecular oxygen, i. e. either ligand exchange reactions, 0-0-bond activation by highly oxophilic metals Sc, Ti, and V, or even complete absence of any reaction are observed (eg. even Cu(C2H4) is unreactive). However, in the case of the iron complexes extensive oxidation reactions are observed. Indeed, not only olefins attached to an iron cation react effectively with molecular oxygen, even stable molecules like benzene and acetone are rapidly oxidized in the presence of Fe+. 

The simplest example of a functional micelle is (49), previously demonstrated to be more effective than its trimethylammonium analogue in both esterolysis and bimolecular elimination reactions. It has now been demonstrated that micelles of (49) are more effective catalysts for the hydrolysis of p-nitrobenzoyl phosphate dianion at high pH than non-functional surfactants. " 2,4-Dinitrochloro- and fluoro-benzene react with micelles of (49) at high pH 10" times faster than with hydroxide ion at a comparable external pH. The initial product is (50) and this in turn is hydrolysed in micelles 2.6 x 10 times faster than is 2,4-dinitrophenyl 2-(trimethylammonium)ethyl ether in water at pH 12. Acyl transfer between p-nitrophenyl acetate and (49) gives an intermediate whose hydrolysis is not micelle catalysed. In contrast to the rate acceleration observed in that case, hydrolysis of p-nitrophenyl acetate is inhibited by micelles of (51) since the phenoxide nucleophile is weak and at the reaction pH its micelles are zwitterionic, not cationic. Synthesis of functional choline-type micelles is facilitated by the use of sulphonate (52), which is reactive towards thiophenoxide in aqueous micelles, but its water-insoluble trifluoromethanesulphonate reacts with a range of anions under phase-transfer conditions. " ... 

Iron, Ruthenium, and Osmium.—Reactions of [(t7-arene)RuCl2]2 with AgBF followed by [2.2]paracyclophane have afforded salts of cationic sandwich complexes in which one (or both) of the arene rings of the cyclophane is(are) n-complexed with an [(j -arene)Ru] + residue. Kinetic studies have been reported of reversible nucleophilic additions of phosphines and phosphites to a benzene ligand of [( -PhH)2M] + (M=Fe, Ru, and Os) reactivity towards addition decreases through the series M = Fe>Ru>Os. ... 

In the section dealing with electrophilic attack at carbon some results on indazole homocyclic reactivity were presented nitration at position 5 (Section 4.04.2.1.4(ii)), sulfon-ation at position 7 (Section 4.04.2.1.4(iii)) and bromination at positions 5 and 7 (Section 4.04.2.1.4(v)). The orientation depends on the nature (cationic, neutral or anionic) of the indazole. Protonation, for instance, deactivates the heterocycle and directs the attack towards the fused benzene ring. A careful study of the nitration of indazoles at positions 2, 3, 5 or 7 has been published by Habraken (7UOC3084) who described the synthesis of several dinitroindazoles (5,7 5,6 3,5 3,6 3,4 3,7). The kinetics of the nitration of indazole to form the 5-nitro derivative have been determined (72JCS(P2)632). The rate profile at acidities below 90% sulfuric acid shows that the reaction involves the conjugate acid of indazole. 

In the absence of die polyether, potassium fluoride is insoluble in benzene and unreactive toward alkyl halides. Similar enhancement of solubility and reactivity of other salts is observed in the presence of crown ethers The solubility and reactivity enhancement result because the ionic compound is dissociated to a tightly complexed cation and a naked anion. Figure 4.13 shows the tight coordination that can be achieved with a typical crown ether. The complexed cation, because it is surrounded by the nonpolar crown ether, has high solubility in the nonpolar media. To maintain electroneutrality, the anion is also transported into the solvent. The cation is shielded from interaction with the anion as a... 

Although this mechanism could explain the inertness of di-t-butyl sulphide towards oxidation due to the absence of a-hydrogen atoms, it was later ruled out by Tezuka and coworkers They found that diphenyl sulphoxide was also formed when diphenyl sulphide was photolyzed in the presence of oxygen in methylene chloride or in benzene as a solvent. This implies that a-hydrogen is not necessary for the formation of the sulphoxide. It was proposed that a possible reactive intermediate arising from the excited complex 64 would be either a singlet oxygen, a pair of superoxide anion radical and the cation radical of sulphide 68 or zwitterionic and/or biradical species such as 69 or 70 (equation 35). 

Certainly pyrazole is very much less reactive than pyrrole toward electrophiles. As the neutral molecule it resembles benzene in reactivity as the anion it is like phenol. Pyrazolium cations are so deactivated that they are reluctant to react with electrophiles. 

Aryl halides are relatively unreactive toward nucleophilic substitution reactions. This lack of reactivity is due to several factors. Steric hindrance caused by the benzene ring of the aryl halide prevents SN2 reactions. Likewise, phenyl cations are unstable, thus making SN1 reactions impossible. In addition, the carbon-halogen bond is shorter and therefore stronger in aryl halides than in alkyl halides. The carbon-halogen bond is shortened in aryl halides for two reasons. First, the carbon atom in aryl halides is sp2 hybridized instead of sp3 hybridized as in alkyl halides. Second, the carbon-halogen bond has partial double bond characteristics because of resonance. 

For the so-called jt-excessive heterocycles, furan, pyrrole, and thiophene, where the heteroatom contributes two electrons to the aromatic sextet, the HOMO is of relatively high energy, compared to that in benzene, which fact confers the familiar high reactivity of these species toward electrophiles. Correspondingly, ionization to give cation-radicals is facile however, such species are not persistent without stabilizing substitution or annelation (see Section III,D,3). Anion-radicals are also known, particularly for thiophene-containing systems (see Part Two this Series, Volume 27, in press). 

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