Chain Free-Radical Reactions

The study of the reactions of the simple free radicals begun by Bodenstein and Lind in 1906 on the kinetics of gas phase reactions showed that the reactions of H2 with CI2 and Bt2 were complex processes/ and a radical chain mechanism for these reactions (equations 14-18) was proposed in 1919 by Christiansen, Herzfeld, and Polanyi/ The theoretical basis for understanding these reactions in terms of free radicals was presented by G.N. Lewis in 1916, with the theory of the electron pair bond, and free radicals, or odd molecules / Further studies on chain reactions including the extension to explosions in gaseous systems were made by Hinshelwood and by Semenovwho shared the Nobel Prize in 1956. 

In 1924 Bonhoeffer demonstrated the formation of atomic hydrogen by an electric discharge (equation 19). The presence of atomic hydrogen was shown by its ability to reduce metal salts (equation 20).  

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W. B. Motherwell, D. Crich Free Radical Chain Reactions in Organic Synthesis (Academic Press 1992)... 

The hydrogenolyaia of cyclopropane rings (C—C bond cleavage) has been described on p, 105. In syntheses of complex molecules reductive cleavage of alcohols, epoxides, and enol ethers of 5-keto esters are the most important examples, and some selectivity rules will be given. Primary alcohols are converted into tosylates much faster than secondary alcohols. The tosylate group is substituted by hydrogen upon treatment with LiAlH (W. Zorbach, 1961). Epoxides are also easily opened by LiAlH. The hydride ion attacks the less hindered carbon atom of the epoxide (H.B. Henhest, 1956). The reduction of sterically hindered enol ethers of 9-keto esters with lithium in ammonia leads to the a,/S-unsaturated ester and subsequently to the saturated ester in reasonable yields (R.M. Coates, 1970). Tributyltin hydride reduces halides to hydrocarbons stereoselectively in a free-radical chain reaction (L.W. Menapace, 1964) and reacts only slowly with C 0 and C—C double bonds (W.T. Brady, 1970 H.G. Kuivila, 1968). 

Termination steps (Section 4 17) Reactions that halt a chain reaction In a free radical chain reaction termination steps consume free radicals without generating new radicals to continue the chain... 

The alkanes have low reactivities as compared to other hydrocarbons. Much alkane chemistry involves free-radical chain reactions that occur under vigorous conditions, eg, combustion and pyrolysis. Isobutane exhibits a different chemical behavior than / -butane, owing in part to the presence of a tertiary carbon atom and to the stability of the associated free radical. 

E. S. Huyser, Free Radical Chain Reactions, Wiley-Interscience, New York, 1970. 

The main industrial use of alkyl peroxyesters is in the initiation of free-radical chain reactions, primarily for vinyl monomer polymerizations. Decomposition of unsymmetrical diperoxyesters, in which the two peroxyester functions decompose at different rates, results in the formation of polymers of enhanced molecular weights, presumably due to chain extension by sequential initiation (204). 

Ethylene Dichloride Pyrolysis to Vinyl Chloride. Thermal pyrolysis or cracking of EDC to vinyl chloride and HCl occurs as a homogenous, first-order, free-radical chain reaction. The accepted general mechanism involves the four steps shown in equations 10—13 ... 

The mechanism by which an oiganic material (RH) undergoes autoxidation involves a free-radical chain reaction (3—5) ... 

Chlorination of Methane. Methane can be chlorinated thermally, photochemicaHy, or catalyticaHy. Thermal chlorination, the most difficult method, may be carried out in the absence of light or catalysts. It is a free-radical chain reaction limited by the presence of oxygen and other free-radical inhibitors. The first step in the reaction is the thermal dissociation of the chlorine molecules for which the activation energy is about 84 kj/mol (20 kcal/mol), which is 33 kJ (8 kcal) higher than for catalytic chlorination. This dissociation occurs sufficiendy rapidly in the 400 to 500°C temperature range. The chlorine atoms react with methane to form hydrogen chloride and a methyl radical. The methyl radical in turn reacts with a chlorine molecule to form methyl chloride and another chlorine atom that can continue the reaction. The methane raw material may be natural gas, coke oven gas, or gas from petroleum refining. 

Chloroform reacts readily with halogens or halogenating agents. Chlorination of the irradiated vapor is beUeved to occur by a free-radical chain reaction (7). 

Thermal chlorination of ethane is generally carried out at 250—500°C. At ca 400°C, a free-radical chain reaction takes place ... 

Selective chlorination of the 3-position of thietane 1,1-dioxide may be a consequence of hydrogen atom abstraction by a chlorine atom. Such reactions of chlorine atoms are believed to be influenced by polar effects, preferential hydrogen abstraction occurring remotely from an electron withdrawing group. The free radical chain reaction may be propagated by attack of the 3-thietanyl 1,1-dioxide radical on molecular chlorine. 

The oxidation of hydrocarbons, including hydrocarbon polymers, takes the form of a free-radical chain reaction. As a result of mechanical shearing, exposure of ultraviolet radiation, attack by metal ions such as those of copper and manganese as well as other possible mechanisms, a hydrocarbon molecule breaks down into two radicals... 

The result of the steady-state condition is that the overall rate of initiation must equal the total rate of termination. The application of the steady-state approximation and the resulting equality of the initiation and termination rates permits formulation of a rate law for the reaction mechanism above. The overall stoichiometry of a free-radical chain reaction is independent of the initiating and termination steps because the reactants are consumed and products formed almost entirely in the propagation steps. 

E. S. Huyser, Free Radical Chain Reactions, Wiley-Interscience, New York, 1970, Chapter 4 G. A. Russell, in Free Radicals, Vol. 1, J. Kochi, ed., John Wiley Sons, New York, 1973, Chapter 7. 

The kinetics of reaction of free radical chain reactions are complicated compared to the second-order kinetics of epoxy and urethane adhesives. Many of these complications offer practical advantages to the process of using acrylic adhesives. 

Free radical chain reactions depend on an easily generated free radical to initiate the chain. One way to generate this radical is to irradiate halogens, such as Ch and Brj. Another way is to add a small amount of an initiator molecule to the reaction mixture, such as AIBN. This molecule, when heated, decomposes into free radicals that react with other molecules to initiate a chain reaction. 

Wawzonek et al. first investigated the mechanism of the cyclization of A-haloamines and correctly proposed the free radical chain reaction pathway that was substantiated by experimental data. "" Subsequently, Corey and Hertler examined the stereochemistry, hydrogen isotope effect, initiation, catalysis, intermediates, and selectivity of hydrogen transfer. Their results pointed conclusively to a free radical chain mechanism involving intramolecular hydrogen transfer as one of the propagation steps. Accordingly, the... 

The free-radical chain reaction may also be terminated by coupling of two carbon-radical species. As solvent carbon tetrachloride is commonly used, where the A-bromosuccinimide is badly soluble. Progress of reaction is then indicated by the decrease of the amount of precipitated NBS and the formation of the succinimide that floats on the surface of the organic liquid layer. 

In order to induce the free-radical chain reaction, a starter compound such as dibenzoyl diperoxide, azo-Zj -(isobutyronitrile) or tcrt-butyl hydroperoxide or UV-light is used. The commercially available, technical grade N-bromosuccinimide contains traces of bromine, and therefore is of slight red-brown color. Since a small amount of elemental bromine is necessary for the radical... 

Bateman, Gee, Barnard, and others at the British Rubber Producers Research Association [6,7] developed a free radical chain reaction mechanism to explain the autoxidation of rubber which was later extended to other polymers and hydrocarbon compounds of technological importance [8,9]. Scheme 1 gives the main steps of the free radical chain reaction process involved in polymer oxidation and highlights the important role of hydroperoxides in the autoinitiation reaction, reaction lb and Ic. For most polymers, reaction le is rate determining and hence at normal oxygen pressures, the concentration of peroxyl radical (ROO ) is maximum and termination is favoured by reactions of ROO reactions If and Ig. 

The presence of one carbonyl group per oligomer molecule was also ascertained. The orange colour of the resin suggested that some minor event during the photopolymerization produced chromophores in small concentrations. The presence of furoin among the products corroborated the proposed mechanism, which was shown not to involve free radical chain reactions. 

Packer and Richardson (1975) and Packer et al. (1980) made use of the fact that electrons can be generated in water by y-radiation from a 60Co source (Scheme 8-29) to induce a free radical chain reaction between diazonium ions and alcohols, aldehydes, or formate ion. It has to be emphasized that the radiolytically formed solvated electron in Scheme 8-29 is only a part of the initiation steps (Scheme 8-30) by which an aryl radical is formed. The aryl radical initiates the propagation steps shown in Scheme 8-31. Here the alcohol, aldehyde, or formate ion (RH2) is the reducing agent (i.e., the electron donor) for the main reaction. The process is a hydro-de-diazoniation. 

For a discussion of the kinetic aspects of radical chain reactions, see Huyser, E.S. Free-Radical Chain Reactions, Ref. 1, p. 39. 

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