Intermediates ionic

The kind of reaction which produces a dead polymer from a growing chain depends on the nature of the reactive intermediate. These intermediates may be free radicals, anions, or cations. We shall devote most of this chapter to a discussion of the free-radical mechanism, since it readily lends itself to a very general treatment. The discussion of ionic intermediates is not as easily generalized. 

Ionic polymerizations, whether anionic or cationic, should not be judged to be unimportant merely because our treatment of them is limited to two sections in this text. Although there are certain parallels between polymerizations which occur via free-radical and ionic intermediates, there are also numerous differences. An important difference lies in the more specific chemistry of the ionic mechanism. While the free-radical mechanism is readily discussed in general terms, this is much more difficult in the ionic case. This is one of the reasons why only relatively short sections have been allotted to anionic and cationic polymerizations. The body of available information regarding these topics is extensive enough to warrant a far more elaborate treatment, but space limitations and the more specific character of the material are the reasons for the curtailed treatment. 

Stereoregular polymerizations strongly resemble anionic polymerizations. We discuss these in greater detail in Chap. 7 because of their microstructure rather than the ionic intermediates involved in their formation. 

Just as anionic polymerizations show certain parallels with the free-radical mechanism, so too can cationic polymerization be discussed in terms of the same broad outline. There are some differences from the anionic systems, however, so the fact that both proceed through ionic intermediates should not be overextended. 

The parameters rj and T2 are the vehicles by which the nature of the reactants enter the copolymer composition equation. We shall call these radical reactivity ratios, although similarly defined ratios also describe copolymerizations that involve ionic intermediates. There are several important things to note about radical reactivity ratios ... 

Cycloadditions are not restricted to the reactions of combinations of neutral dienes and dienophiles. There are examples of corresponding reactions involving ionic intermediates. The addition of 2-methylallyl cation to cyclopentadiene is an example ... 

Nevertheless, many free-radical processes respond to introduction of polar substituents, just as do heterolytic processes that involve polar or ionic intermediates. The substituent effects on toluene bromination, for example, are correlated by the Hammett equation, which gives a p value of — 1.4, indicating that the benzene ring acts as an electron donor in the transition state. Other radicals, for example the t-butyl radical, show a positive p for hydrogen abstraction reactions involving toluene. ... 

Many of the reactions of BF3 are of the Friedel-Crafts type though they are perhaps not strictly catalytic since BF3 is required in essentially equimolar quantities with the reactant. The mechanism is not always fully understood but it is generally agreed that in most cases ionic intermediates are produced by or promoted by the formation of a BX3 complex electrophilic attack of the substrate by the cation so produced completes the process. For example, in the Friedel-Crafts-type alkylation of aromatic hydrocarbons ... 

Sn2 attack of the electron-rich platinum(O) on the alkyl halide to give the Ptn(R)X species directly, possibly via an ionic intermediate. 

Diacyl peroxides may also undergo non-radical decomposition via the carboxy inversion process to form an acylcarbonate (Scheme 3.27).46 The reaction is of greatest importance for diaroyl peroxides with electron withdrawing substituents and for aliphatic diacyl peroxides (36) where R is secondary, tertiary or ben/,yl.157 The reaction is thought to involve ionic intermediates and is favored in polar solvents 57 and by Lewis acids.158 Other heterolytic pathways for peroxide decomposition have been described.150... 

Peroxyeslers may undergo non-radical decomposition via ibe Criegee rearrangement (Scheme 3.35). This process is analogous to the earboxy inversion process described for diacyl peroxides (see 3.3.2.1,3) and probably involves ionic intermediates. 

The mechanism of the polymerization contains ionic intermediate steps. The free H+ goes to a carbenium ion and, as shown in route B, rearranges to form tetrapropylene. It is highly likely that this actual tetrapropylene exists only in very small concentrations. The product variety is explained by the rearrangement of the carbenium ion to dodecene isomers according to route C. In addition, short-chain olefins formed by fragmentation (route D). Polymerization proceeds at almost 100% to mono olefins. Aromatics, paraffins, and diolefins exist only in trace amounts. The propylene tetramer is best characterized by its distillation range. 

Assigning a mechanism for the formation of products resulting from ionic intermediates is aided by our knowledge of the probable primary ions and the elementary ion-molecule reactions which they may undergo. The second subject to be examined is the applicability of fragmentation patterns and mass spectrometric ion-molecule reaction studies to radiolysis conditions. Lastly, the formation and the chemistry of the ionic species in ethylene radiolysis will be summarized. 

The arguments which have been advanced to support mechanisms of product formation involving ionic intermediates can be classified into two principal groups. 

TTigh pressure mass spectrometry has recently provided much detailed kinetic data (5, 12, 13, 14, 15, 17, 22, 24, 26, 29) concerning ionic reactions heretofore unobtainable by other means. This information has led to increased understanding of primary reaction processes and the fate of ionic intermediates formed in these processes but under conditions distinctly different from those which prevail in irradiated gases near room temperature and near atmospheric pressure. Conclusive identification and measurements of the rate constants of ionic reactions under the latter conditions remain as both significant and formidable problems. 

A mechanism was proposed31 for the formation of di-D-fructose dianhydrides from inulin and fructose. It was suggested that a-D-Fru/-1,2 2,1 - 3-D-Fru/ [difructose anhydride I (5)] formed first and then isomerized via ionic intermediates to produce the remaining products. Important support for the concept of the reversibility of the isomerization was the observation that ot-D-Frup-1,2 2,1 - 3-D-Frup (4) and p-D-Frup-1,2 2,1 - 3-D-Frup produced, upon treatment with HF, the same product mixture as did D-fructose. 

Several investigations into the photochemistry of eucarvone have shown that upon irradiation it isomerizes to a mixture of products whose composition is solvent-dependent (Biichi and Burgess, I960 Hurst and Whitham, 1963 Shuster et al., 1964 Shuster and Sussman, 1970 Takino and Hart, 1970 Hart and Takino, 1971). Ionic intermediates have been invoked in the case of polar solvents (Chapman, 1963). Irradiation of protonated eucarvone 58 in fluorosulfonic acid seems to... 

The mechanism for reaction 13 is not well established yet, but it is likely to proceed through ionic intermediates (11) the Cl atom in chlorine nitrate is slightly electropositive, so that it readily combines with negative chloride ions to produce CI2 the HQ on ice is expected to be at least partially ionized. We have found that HCl has a very high mobility on the ice surface, so that even small amounts of HCl will enable reaction 13 to occur. It is also possible for this reaction to proceed in two steps the initial step is the reaction of chlorine nitrate with ice it is followed by the reaction of the product HOCl with HCl on the ice substrate ... 

Whereas the three possible selectivities, stereo-, regio- and chemo-selectivity, of bromine addition are determined in steps posterior to the formation of the ionic intermediate. Bromine addition is, therefore, more complex than bromine substitution, as regards the variety of the selectivities and as regards the mechanistic aspects which determine the product formation. 

Many mechanistic results on this electrophilic addition are available but most of them deal with the first steps of the reaction in which the ionic intermediate is formed, rather than with the last steps in which the products are obtained by nucleophilic attack on this intermediate (ref. 2). The present paper reports results on the selectivity of olefin bromination, which have been obtained more or less systematically with a view to improving the existing rules which are too naive to be useful in synthesis (ref. 3). 

The simplified mechanism shown in Scheme 2 focuses attention on the ionic intermediate which is presented in the usual form of a bromonium ion although it is now well known that it can be an open p-bromocarbocation (ref. 4). 

When a substituent is able to resonantly stabilize the positive charge of the ionic intermediate, there is no bromine bridging and the intermediate is an open P-bromocarbocation. These carbocations have been shown to occur in the bromination of a-methylstilbenes (ref. 9), 1 and 2, and of a variety of enol ethers (ref. 10) and acetates (ref. 11). 

Furthermore, a well detectable conductivity has been measured in solutions of Bt2 and certain olefins, like carbamazepine, pointing to the accumulation of ionic intermediates during the bromination process (ref. 16). 

Reversible formation of ionic intermediates in halogenated solvents has been suggested to be due to the weakly nucleophilic character of the counteranion, the tribromide ion, which should dissociate into nucleophilic bromide and free bromine before reacting with the bromonium ion (refs. 11,25,26). In order to check this hypothesis the product distribution of the c/s-stilbene bromination in chloroform was investigated (ref. 27). In the latter solvent the formation constant of Br3 is considerably lower than in DCE, Kf = 2.77 (0.13) x 10 against > 2 x 107 M 1. (ref. 28). As a consequence, at 10 3 M [Br2] relevant amounts of bromide ions are present as counteranion of the bromonium intermediate. Nevertheless, the same trend for the isomerization of cis- to rran -stilbene, as well as an increase of... 

Effect of Solvent on El versus E2 versus ElcB. With any reaction a more polar environment enhances the rate of mechanisms that involve ionic intermediates. For neutral leaving groups, it is expected that El and ElcB... 

The aziridine aldehyde 56 undergoes a facile Baylis-Hillman reaction with methyl or ethyl acrylate, acrylonitrile, methyl vinyl ketone, and vinyl sulfone [60]. The adducts 57 were obtained as mixtures of syn- and anfz-diastereomers. The synthetic utility of the Baylis-Hillman adducts was also investigated. With acetic anhydride in pyridine an SN2 -type substitution of the initially formed allylic acetate by an acetoxy group takes place to give product 58. Nucleophilic reactions of this product with, e. g., morpholine, thiol/Et3N, or sodium azide in DMSO resulted in an apparent displacement of the acetoxy group. Tentatively, this result may be explained by invoking the initial formation of an ionic intermediate 59, which is then followed by the reaction with the nucleophile as shown in Scheme 43. 

Additional work on alkyl platinum reactions has been completed which mostly supports the generality of these observed insertion reactions. Treichel and Wagner 153) have varied the choice of phosphine ligand utilizing the complexes Pt(phos)2(CH3)X (phos = PEtj, X = Br, I and phos = PPhMe2, X = I) both ionic intermediate and inserted products were obtained. 

Yamamoto and Yamazaki 171) carried out reactions of Pt(PEt3)2CHjI and Pt(PPhMe2)(CH2CjH5)I with tert-butyl and cyclohexyl isocyanides. These reactions gave small yields of the ionic intermediate species, which readily reverted to the appropriate iminoacyl complexes. In reactions of analogous chloride complexes the intermediate species was not isolated. It is suggested on the basis of PMR data that these iminoacyl complexes are five-coordinate (see above). 

Why does the presence of peroxides cause the addition to be anb -Markovnikov In order to understand the answer to this question, we will need to explore the mechanism in detail. This reaction follows a mechanism that involves radical intermediates (such as Br ), rather than ionic intermediates (such as Br ). Peroxides are used to generate bromine radicals, in the following way ... 

Enantiocontrol of the photocyclization of Ar-methyl-AT-phenyl-3-amino-2-cyclohexen-l-one (151a,b) to the corresponding AT-methylhexahydro-4-car-bazolones (153a,b) via the dipolar ionic intermediate (152a,b) (Scheme 22) was also accomplished by photoirradiation of 1 1 inclusion complexes of 151 a,b with the chiral hosts lOa-c. Of the complexes prepared, 10a-151a, 10a-151b,... 

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