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Substitution reactions ionic

In some cases, the Q ions have such a low solubility in water that virtually all remain in the organic phase. ° In such cases, the exchange of ions (equilibrium 3) takes place across the interface. Still another mechanism the interfacial mechanism) can operate where OH extracts a proton from an organic substrate. In this mechanism, the OH ions remain in the aqueous phase and the substrate in the organic phase the deprotonation takes place at the interface. Thermal stability of the quaternary ammonium salt is a problem, limiting the use of some catalysts. The trialkylacyl ammonium halide 95 is thermally stable, however, even at high reaction temperatures." The use of molten quaternary ammonium salts as ionic reaction media for substitution reactions has also been reported. " " ... [Pg.455]

In its original form the Hammett equation was appropriate for use with para and meta substituted compounds where the reaction site is separated from the aromatic group by a nonconjugating side chain. Although there have been several extensions and modifications that permit the use of the Hammett equation beyond these limitations, it is not appropriate for use with ortho substituted compounds, since steric effects are likely to be significant with such species. The results obtained using free radical reactions are often poor, and the correlation is more appropriate for use with ionic reactions. For a detailed discussion of the Hammett equation and its extensions, consult the texts by Hammett (37), Amis and Hinton (12), and Johnson (47). [Pg.239]

SRV1 reactions of gem-halonitroalkanes with the anion of active methylene compounds followed by deethoxycarbonylation and denitration provide useful methods for preparing highly substituted olefins, as shown in Eq. 7.140.186 Because the SRN I reaction is less sensitive to steric effects than the ionic reaction, such reaction as that shown in Eq. 7.140 has merits over other... [Pg.224]

Ionic Reactions—Nucleophilic Substitution and Elimination Reactions of Alkyl Halides... [Pg.221]

It is clear that reactions suitable for use in titrimetric procedures must be stoichiometric and must be fast if a titration is to be carried out smoothly and quickly. Generally speaking, ionic reactions do proceed rapidly and present few problems. On the other hand, reactions involving covalent bond formation or rupture are frequently much slower and a variety of practical procedures are used to overcome this difficulty. The most obvious ways of driving a reaction to completion quickly are to heat the solution, to use a catalyst, or to add an excess of the reagent. In the last case, a hack titration of the excess reagent will be used to locate the stoichiometric point for the primary reaction. Reactions employed in titrimetry may be classified as acid-base oxidation-reduction complexation substitution precipitation. [Pg.192]

When chlorination or bromination of alkenes is carried out in the gas phase at high temperature, addition to the double bond becomes less significant and substitution at the allylic position becomes the dominant reaction.153-155 In chlorination studied more thoroughly a small amount of oxygen and a liquid film enhance substitution, which is a radical process in the transformation of linear alkenes. Branched alkenes such as isobutylene behave exceptionally, since they yield allyl-substituted product even at low temperature. This reaction, however, is an ionic reaction.156 Despite the possibility of significant resonance stabilization of the allylic radical, the reactivity of different hydrogens in alkenes in allylic chlorination is very similar to that of alkanes. This is in accordance with the reactivity of benzylic hydrogens in chlorination. [Pg.590]

In what follows we will be concerned with the rates of ionic reactions under nonequilibrium conditions. We shall use the term nucleophile repeatedly and we want you to understand that a nucleophile is any neutral or charged reagent that supplies a pair of electrons, either bonding or nonbonding, to form a new covalent bond. In substitution reactions the nucleophile usually is an anion, Y 0 or a neutral molecule, Y or HY . The operation of each of these is illustrated in the following equations for reactions of the general compound RX and some specific examples ... [Pg.210]

A beautiful extension of this reaction has recently been communicated by Nozaki, Oshima, and Utimo-to.184 These workers simply admixed f-butyl iodide (3 equiv.), benzaldehyde (1 equiv.), methyl vinyl ketone (1 equiv.) and triethylborane (1 equiv.) in benzene (Scheme 60). After 5 min at 25 C, the reaction was subjected to standard extractive work-up and the crude product was purified by chromatography to give (54) in 63% yield. If methanol is substituted for benzaldehyde, the protonated product (55) is isolated in 79% yield. Although enones are equivalents of synthon (56), such a direct coupling of radical and ionic reactions had not been achieved previously. [Pg.756]

Direct substitution reactions of other diamonoid hydrocarbons have not been studied extensively. Triamantane, for example, remains relatively unavailable at this time. Moreover, the low symmetry of this molecule discourages attempts to prepare triamantane derivatives by direct substitution. The highly selective ionic reactions would most certainly not give all possible isomers. Less selective substitutions (e.g. free radical, see below), on the other hand, might enable the preparation of most isomers but separation of the product mixtures would undoubtedly be extremely tedious. [Pg.65]

In contrast to the highly specific ionic reactions of diamonoid hydrocarbons discussed above, free radical substitutions are much less selective. Thus, free radical reactions provide a method for the preparation of a greater number of the possible isomers of a given hydrocarbon than might be available by ionic processes. The complex product mixtures which result, however, are generally difficult to separate. Consequently, there are few examples of the synthesis of specific derivatives of diamonoid hydrocarbons by this method. [Pg.65]

A slightly more rational way to say the same thing is that we do really know which component supplies the HOMO ( nucleophile ) and which the LUMO ( electrophile ). The enone 38 is naturally electrophilic as in 43 and 45, especially when bound to the Lewis acid. If the diene 37 acted as a nucleophile, it would give the more highly substituted allylic cations 44 and 46. The Diels-Alder is not an ionic reaction and 44 and 46 are not intermediates but the HOMO and LUMO that determine the regiochemistry in the imaginary ionic reactions 43 and 45 also determine the regiochemistry of the pericyclic reactions. [Pg.125]

A similar cyclisation of an alkene derived from geranyl acetate 24 by dihydroxylation and formation of the epoxide 26 leads to a substituted cyclohexane 28. The Lewis acid ZrCU is used to open the epoxide and the alkene attacks intramolecularly 27 to give eventually the ryn-compound 28 with both substituents equatorial. The alignment of the alkene and the epoxide in a chair conformation 27a is responsible for the diastereoselectivity Note the regioselectivity the less substituted end of the alkene attacks the more substituted end of the epoxide 27. These are just two examples of the very many ordinary ionic reactions that can be used to make six-membered rings. [Pg.271]

The photostimulated reactions of thiolate anions with 2-halo-2 -nitropropane derivatives yield both oc-nitrosulphides via an S l pathway and disulphides (equation 71a)282 284. In contrast with the case of the oxidative dimerisation products of the mono-enolates, the disulphides are formed via an ionic mechanism nucleophilic attack by the thiolate anion on the a-halogen and subsequent reaction of a second thiolate with the sulphenyl halide. As expected for such a process, disulphide formation is favoured (and thus a-nitrosulphide formation is disfavoured) the more nucleophilic the thiolate (i.e. derived from a less acidic thiol) and the easier the abstraction of the halo-substituent (i.e. I > Br > Cl). Use of the protic solvent methanol instead of the usual dipolar aprotic solvents for the reaction of equation 71a is detrimental to the yield of the S l substitution products exclusively disulphides are formed285 (equation 71b). Methanol solvation probably retards the dissociation of the radical anion intermediate in the SRN reaction, into radical and anion, and hence retards the chain reaction relative to the ionic reaction. The non-nucleophilic methylsulphinate ion gives only an S l reaction product with 2-bromo-2-nitropropane286. [Pg.894]

Note that both mechanisms for the addition of HBr to an alkene (with and without peroxides) follow our extended statement of Markovnikov s rule In both cases, the electrophile adds to the less substituted end of the double bond to give the more stable intermediate, either a carbocation or a free radical. In the ionic reaction, the electrophile is H+. In the peroxide-catalyzed free-radical reaction, Br is the electrophile. [Pg.336]

It mey not be immediately obvious why the sizes of the coefficients swap round, but you can think of it as we did before by considering an ionic reaction of the alkene. If we want to know about the alkene s LUMO you have to consider what would happen if you could add nucleophiles to it. Of course, with an electron-rich afkene this is a very rare reaction because the LUMO is high in energy. But some organometalfic additions to unactivated afkenes are known, and they attack the more substituted end in order to locate a C-metal bond at the less substituted carbon. The LUMO has a greater coefficient at the more substitutad carbon. [Pg.928]

In addition to the above-mentioned ring contractions and trans-annular bonding of compounds of the type 10 in ionic reactions, photo-induced valence tautomerism has also been noted.38 Thus 10 or the various 2-substituted compounds can be converted to 44.35... [Pg.29]

If we wish to direct the attack of halogen to the alkyl portion of an alkene molecule, then, we choose conditions that are favorable for the free-radical reaction and unfavorable for the ionic reaction. Chemists of the Shell Development Company found that, at a temperature of 500-600°, a mixture of gaseous propylene and chlorine yields chiefly the substitution product, 3-chloro-l-propene, known as allyl chloride (CH2=CH—CH2— = allyl). Bromine behaves similarly. [Pg.209]

Perhaps the most convincing evidence for the play of polar forces comes from copolymerization of a series of ring-substituted styrenes here relative reactivities toward a variety of monomers not only fall into a pattern consistent with the familiar electronic effects of the substituents, but show the same quantitative relationships (the Hammett sigma-rho relationship. Sec. 18.11) as do ionic reactions dissociation of carboxylic acids, for example, or hydrolysis of esters. [Pg.1036]

An alternative method for terminal halide by ionic reactions. Thus, nucleophilic substitution was examined with compounds EC-16 to EC-23. For example, an amino alcohol (EC-16) in DMSO at room temperature gives polystyrene with hydroxyl groups.280 350 However, an amino alcohol with a longer spacer (EC-17) should be employed for poly(MA) to avoid multiple alcohol functionalities.280... [Pg.488]

Non-equilibrium behavior may also affect some ionic reactions. In our examples we have therefore emphasized processes involving substitution-labile ions rather than substitution-inert ones. Problems of slow kinetics are especially common with ionic redox reactions, in which case equilibrium considerations indicate what is theoretically feasible, but not necessarily what is truly factual. This is why so many quantitative electrometric methods are based on either silver or mercury, two metals on which the metal/metal ion equilibrium is usually established so rapidly that the underlying kinetics can be neglected in routine analytical measurements, and on platinum, where the same applies to many electron transfer processes between soluble redox couples. [Pg.222]

There are in principle three possibilities for reaction of halogens with aromatic hydrocarbons, namely, addition, substitution in the nucleus, and substitution in a side chain. The last of these is discussed on pages 152 and 157. Substitution of benzene by chlorine or bromine is an ionic reaction,114 whereas photochemical or peroxide-catalyzed addition of these halogens involves a radical-chain mechanism.115 Substitution in the side chain also proceeds by a radical mechanism,116 addition rather than side-chain substitution being favored by higher chlorine concentrations.115... [Pg.117]


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Ionic reactions

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