Site of attack

The methyl groups direct the entering group primarily to the ortho and para positions (Table 3). The preferred site of attack by an electrophile on pseudocumene and hemimellitene is shown as follows (13) however, steric hindrance can cause a shift such as a / fX butylation of hemimellitene predominandy at the 5-position. Mesitylene, all three tetramethylbenzenes, and pentamethylbenzene can only form one mono- and one disubstituted isomer (except pentamethylbenzene). Hence, high purity derivatives are possible. 

Attack of an unsubstituted benzene ring can lead to only one monosubstitution product. However, when electrophilic attack occurs at a benzene ring already containing a group, there are three possible sites of attack. 

The main features of the effect of structure on the site of attack are summarized in Table 3, and can be understood in.terms of a borderline 5n2 (59CRV737) transition state (48) which somewhat resembles an 5n1 transition state in charge distribution because C—O bond breaking runs ahead of Nu—C bond making. 

Treatment of thiiranes with lithium aluminum hydride gives a thiolate ion formed by attack of hydride ion on the least hindered carbon atoms (76RCR25), The mechanism is 5n2, inversion occurring at the site of attack. Polymerization initiated by the thiolate ion is a side reaction and may even be the predominant reaction, e.g. with 2-phenoxymethylthiirane. Use of THF instead of ether as solvent is said to favor polymerization. Tetrahydroborates do not reduce the thiirane ring under mild conditions and can be used to reduce other functional groups in the presence of the episulfide. Sodium in ammonia reduces norbornene episulfide to the exo thiol. 

The chemical reactivity of these two substituted ethylenes is in agreement with the ideas encompassed by both the MO and resonance descriptions. Enamines, as amino-substituted alkenes are called, are vety reactive toward electrophilic species, and it is the p carbon that is the site of attack. For example, enamines are protonated on the carbon. Acrolein is an electrophilic alkene, as predicted, and the nucleophile attacks the P carbon. 

As previously mentioned, some urethanes can biodegrade easily by hydrolysis, while others are very resistant to hydrolysis. The purpose of this section is to provide some guidelines to aid the scientist in designing the desired hydrolytic stability of the urethane adhesive. For hydrolysis of a urethane to occur, water must diffuse into the bulk polymer, followed by hydrolysis of the weak link within the urethane adhesive. The two most common sites of attack are the urethane soft segment (polyol) and/or the urethane linkages. Urethanes made from PPG polyols, PTMEG, and poly(butadiene) polyols all have a backbone inherently resistant to hydrolysis. They are usually the first choice for adhesives that will be exposed to moisture. Polyester polyols and polycarbonates may be prone to hydrolytic attack, but this problem can be controlled to some degree by the proper choice of polyol. 

LUMO for protonated methyl acetate reveals likely site of attack by water. 

In the frozen MO approximation the last terms are zero and the Fukui functions are given directly by the contributions from the HOMO and LUMO. The preferred site of attack is therefore at the atom(s) with the largest MO coefficients in the HOMO/LUMO, in exact agreement with FMO theory. The Fukui function(s) may be considered as the equivalent (or generalization) of FMO methods within Density Functional Theory (Chapter 6). 

Crevice corrosion and pitting have a number of features in common, and it has been stated that pitting may be regarded as crevice corrosion in which the pit forms its own crevice however, whereas a macroscopic heterogeneity determines the site of attack in crevice corrosion, the sites of attack in pitting are determined by microscopic or sub-microscopic features in the passive film (5 Sections 1.3 and 1.5). 

The rate of radical addition is most dramatically affected by substituents either at the site of attack or at the radical center. Remote substituents generally have only a small influence on the stereochemistry and regiospecificity of addition unless these groups are very bulky or the geometry of the molecules is constrained (e.g. intramolecular addition - Section 1,2.4). 

It was proposed that the transition state requires approach of the radical directly above the site of attack and perpendicular to the plane containing the carbon-carbon double bond. An examination of molecular models shows that for the 3-butenyl and 4-pentenyl radicals (16, =1,2) such a transition state can only be reasonably achieved in < Xf>-cyclization (i.e. 16—> 15). With the 5-hexcnyl and 6-heptenyl radicals (16, w=3,4), the transition state for exo-cyclization (16- 15) is more easily achieved than that for enc/o-cyclization (i.e. 16 — 17). 

Steric factors fall into four main categories 27 (a) The release or occurrence of steric compression due to rehybridization in the transition state where the attacking radical and site of attack are each undergoing rehybridization (from sp1 - sp1 and sp1 - sp respectively for aliphatic carbons - refer Figure 1.6). As a consequence, substituents on the attacking radical are brought closer together while those at the site of attack... 

Figure 1.8 Preferred site of attack in hydrogen abstraction by various radicals. 1.3.4 Stereoelectronic Factors...

In fused ring systems, the positions are not equivalent and there is usually a preferred orientation even in the unsubstituted hydrocarbon. The preferred positions may often by predicted as for benzene rings. Thus it is possible to draw more canonical forms for the arenium ion when naphthalene is attacked at the a position than when it is attacked at the p position, and the a position is the preferred site of attack,though, as previously mentioned (p. 682), the isomer formed by substitution at the p position is thermodynamically more stable and is the product if the reaction is reversible and equilibrium is reached. Because of the more extensive delocalization of charges in the corresponding arenium ions, naphthalene is more reactive than benzene and substitution is faster at both positions. Similarly, anthracene, phenanthrene, and other fused polycyclic aromatic hydrocarbons are also substituted faster than benzene. 

For a discussion on the preferred site of attack for many ring systems, see de la Mare, P.B.D. Ridd, J.H. Aromatic Substitution Nitration and Halogenation Academic Press NY, 1959, p. 169. 

The main differences between these oxidations and those of monofunctional compounds are (i) the greater number of possible sites of attack, (i7) the more frequent modification of kinetics by complex formation and in) the almost inevitable greater reactivity. 

Two contrasting conclusions have been reported in the reactions of lithium aluminium hydride in THF with phosphine oxides and phosphine sulphides respectively. The secondary oxide, phenyl-a-phenylethylphos-phine oxide (42), has been found to be racemized very rapidly by lithium aluminium hydride, and this observation casts some doubt on earlier reports of the preparation of optically active secondary oxides by reduction of menthyl phosphinates with this reagent. A similar study of the treatment of (/ )-(+ )-methyl-n-propylphenylphosphine sulphide (43) with lithium aluminium hydride has revealed no racemization. These results have been rationalized on the basis of the preferred site of attack of hydride on the complexed intermediate (44), which, in the case of phosphine oxides (X = O), is at phosphorus, and in the case of the sulphides (X = S), is at sulphur. Such behaviour is comparable to that observed during the reduction of phosphine oxides and sulphides with hexachlorodisilane. ... 

Attempts to achieve selective oxidations of hydrocarbons or other compounds when the desired site of attack is remote from an activating functional group are faced with several difficulties. With powerful transition-metal oxidants, the initial oxidation products are almost always more susceptible to oxidation than the starting material. When a hydrocarbon is oxidized, it is likely to be oxidized to a carboxylic acid, with chain cleavage by successive oxidation of alcohol and carbonyl intermediates. There are a few circumstances under which oxidations of hydrocarbons can be synthetically useful processes. One group involves catalytic industrial processes. Much effort has been expended on the development of selective catalytic oxidation processes and several have economic importance. We focus on several reactions that are used on a laboratory scale. 

In some cases the site of attack is in no doubt, e.g., 9 adds PMe3 at the carbyne carbon in an orbital-controlled reaction (29,31) ... 

Bromine is less reactive toward alkanes in general than chlorine, but bromine is more selective in the site of attack when it does react. 

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