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Radical addition reactions alkenes

The same high reactivity of radicals that makes possible the alkene polymerization we saw in the previous section also makes it difficult to carry out controlled radical reactions on complex molecules. As a result, there are severe limitations on the usefulness of radical addition reactions in the laboratory. Tn contrast to an electrophilic addition, where reaction occurs once and the reactive cation intermediate is rapidly quenched in the presence of a nucleophile, the reactive intermediate in a radical reaction is not usually quenched, so it reacts again and again in a largely uncontrollable wav. [Pg.243]

Several other types of addition reactions of alkenes are also of importance and these are discussed elsewhere. Nucleophilic additions to electrophilic alkenes are covered in Section 2.6 and cycloadditions involving concerted mechanisms are encountered in Sections 6.1 to 6.3. Free radical addition reaction are considered in Chapter 11. [Pg.290]

The recognition of anti-Markownikoff orientation when HBr was added to alkenes in the presence of traces of peroxides or air lead to the discovery of the large and important class of free radical addition reactions to unsaturated systems89). The ant Markownikoff orientation of these reactions i.e., the preference of initial radical at-... [Pg.22]

The dependence of relative rates in radical addition reactions on the nucleophilicity of the attacking radical has also been demonstrated by Minisci and coworkers (Table 7)17. The evaluation of relative rate constants was in this case based on the product analysis in reactions, in which substituted alkyl radicals were first generated by oxidative decomposition of diacyl peroxides, then added to a mixture of two alkenes, one of them the diene. The final products were obtained by oxidation of the intermediate allyl radicals to cations which were trapped with methanol. The data for the acrylonitrile-butadiene... [Pg.624]

The regioselectivity in radical addition reactions to alkenes in general has successfully been interpreted by a combination of steric and electronic effects1815,47. In the absence of steric effects, regiochemical preferences can readily be explained with FMO theory. The most relevant polyene orbital for the addition of nucleophilic radicals to polyenes will be the LUMO for the addition of electrophilic orbitals it will be the HOMO. Table 10 lists the HOMO and LUMO coefficients (without the phase sign) for the first three members of the polyene family together with those for ethylene as calculated from Hiickel theory and with the AMI semiempirical method48. [Pg.630]

Polymers can be formed from compounds containing a c=c double bond. Alkenes, such as ethene, can undergo addition polymerisation to form a polymer. A polymer is a compound consisting of very long chain molecules built up from smaller molecular units, called monomers. The polymerisation of ethene, to form poly(ethene), is a free radical addition reaction. [Pg.102]

Dienamides such as 167 react by a different reaction pathway168, namely by addition of the amide oxygen to the alkene by a radical addition reaction (equation 111). [Pg.727]

Electron transfer from the alkene leads to a radical cation that can undergo coupling (Scheme la). The radical cation can also react with the nucleophilic heteroatom of a reagent to afford addition or substitution products (Scheme lb). Adducts can be likewise obtained by oxidation of the nucleophile to a radical that undergoes radical addition. Reactions between alkenes and nucleophiles can be realized too with chemical oxidants that are regenerated at the anode (mediators) (see Chapter 15). Finally, cycloadditions between alkenes can be initiated by a catalytic anodic electron transfer. These principal reaction modes are subsequently illustrated by selected conversions. [Pg.134]

The reactivity of a range of alkenes in addition reactions of peroxyl radicals has been reported. Parameters that described the relationship between the activation energy and enthalpy were calculated. An activation energy of 82 kJ moP was determined for the addition of alkylperoxy radicals to isolated C=C bonds, rising by 8.5kJmor when the alkene was conjugated with an aromatic substituent. [Pg.145]

We have here a mixture of electrophilic and radical addition reactions to alkenes. Remember the guidelines that radical reactions are characterized by the inclusion of radical initiators, such as light or peroxides. In the absence of such initiators, consider only the alternative electrophilic mechanisms. [Pg.638]

Because the addition steps are generally fast and consequently exothermic chain steps, their transition states should occur early on the reaction coordinate and therefore resemble the starting alkene. This was recently confirmed by ab initio calculations for the attack at ethylene by methyl radicals and fluorene atoms. The relative stability of the adduct radicals therefore should have little influence on reacti-vity 2 ). The analysis of reactivity and regioselectivity for radical addition reactions, however, is even more complex, because polar effects seem to have an important influence. It has been known for some time that electronegative radicals X-prefer to react with ordinary alkenes while nucleophilic alkyl or acyl radicals rather attack electron deficient olefins e.g., cyano or carbonyl substituted olefins The best known example for this behavior is copolymerization This view was supported by different MO-calculation procedures and in particular by the successful FMO-treatment of the regioselectivity and relative reactivity of additions of radicals to a series of alkenes An excellent review of most of the more recent experimental data and their interpretation was published recently by Tedder and... [Pg.26]

C-Glycoside synthesis may be achieved in twro ways. Intermolecular radical addition reactions are observed with (i) polarized, electron-deficient alkenes, (ii) alkenes that provide a high level of stabilization to the initial radical adduct and (in) substrates that undergo a facile fragmentation (e.g. allyl stannanes). Additions to less reactive substrates, though not favored for intermolecular processes, are observed if the two components are tethered in an intramolecular array. [Pg.46]

ALKENES AND ALKYNES I. IONIC AND RADICAL ADDITION REACTIONS... [Pg.350]

Alkenes and Alkynes I. Ionic and Radical Addition Reactions... [Pg.352]

A significant observation concerning bromine addition is that it and many of the other reactions listed on page 360 proceed in the dark and are not influenced by radical inhibitors. This is evidence against a radical-chain mechanism of the type involved in the halogenation of alkanes (Section 4-4D). However, it does not preclude the operation of radical-addition reactions under other conditions, and, as we shall see later in this chapter, bromine, chlorine, and many other reagents that commonly add to alkenes by ionic mechanisms also can add by radical mechanisms. [Pg.362]

Alkenes and Alkynes I. Ionic and Radical Addition Reactions more stable, the 1-bromo-2-propyl radical, 5, or the 2-bromo-1 -propyl radical, 6 ... [Pg.388]


See other pages where Radical addition reactions alkenes is mentioned: [Pg.338]    [Pg.23]    [Pg.276]    [Pg.126]    [Pg.486]    [Pg.328]    [Pg.329]    [Pg.331]    [Pg.657]    [Pg.277]   
See also in sourсe #XX -- [ Pg.758 ]




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