A free-radical additions

In the presence of peroxides, hydrogen bromide adds to the double bond of styrene with a regioselectivity opposite to Markovnikov s nrle. The reaction is a free-radical addition, and the regiochemistiy is governed by preferential fonnation of the more stable radical. 

A5-hexenyl substituent, extensive cyclization occurs to yield the cyclopentylcarbinyl product from the yields of uncyclized and cyclized products for A5-hexenylmercury chloride, the rate constants for equation 50 have been estimated (vide supra). The SH2 reaction 49 has also been invoked to be the key step in the alkylation of -substituted styrenes by a free-radical addition-elimination sequence, namely96... 

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. 

The /-BuO abstracts H- from malonate in the initiation part. A free radical addition mechanism like the one in problem 5.3 ensues. 

It is possible to obtain anti-Markovnikov products when HBr is added to alkenes in the presence of free radical initiators, e.g. hydrogen peroxide (HOOH) or alkyl peroxide (ROOR). The free radical initiators change the mechanism of addition from an electrophilic addition to a free radical addition. This change of mechanism gives rise to the anh-Markovnikov regiochemistry. For example, 2-methyl propene reacts with HBr in the presence of peroxide (ROOR) to form 1-bromo-2-methyl propane, which is an anh-Markovnikov product. Radical additions do not proceed with HCl or HI. 

In the presence of copper(I) chloride, FC-113a adds to silyl enol ethers affording adducts which can be transformed into the /1-chloro-/i-trifluoromethyl enones in moderate yields [100]. The carbon-carbon bond is formed via a free radical addition reaction (Eq. 28). Free radical addition mediated by iron pentacarbonyl was also described recently during a synthesis of a modified pyrethroid [101]. 

An alkyl group (primary, secondary, or tertiary) can be added to the oxime ether CHr=NOCH2Ph by treatment with the appropriate alkyl halide and an equimolar amount of bis(trimethylstannyl)benzopicolinate.483 This reaction, which is a free radical addition, is another way to extend a chain by one carbon. 

Common thermosets are cured by a free radical addition mechanism. These types of composites are cured by heat initiators, such as peroxides, or by photo initiators, such as a-diketones. A characteristic of cured acrylates is large shrinkage in the course of polymerization, which is undesirable for many uses. Another undesirable characteristic of acrylates is the formation of an oxygen-inhibited layer on the surface upon curing. 

Resin solidification (curing) occurs by a free radical addition mechanism at the double bonds. That is why no by-products are formed. Curing compositions based on polyester resins contain a large number of different components (resins, initiators, accelerators, monomers, oligomers, fillers, etc), which may have various chemical structures, and may be used in various proportions. 

Essentially, TFE in gaseous state is polymerized via a free radical addition mechanism in aqueous medium with water-soluble free radical initiators, such as peroxy-disulfates, organic peroxides, or reduction-activation systems.15 The additives have to be selected very carefully since they may interfere with the polymerization. They may either inhibit the process or cause chain transfer that leads to inferior products. When producing aqueous dispersions, highly halogenated emulsifiers, such as fully fluorinated acids,16 are used. If the process requires normal emulsifiers, these have to be injected only after the polymerization has started.17 TFE polymerizes readily at moderate temperatures (40 to 80°C) (104 to 176°F) and moderate pressures (0.7 to 2.8 MPa) (102 to 406 psi). The reaction is extremely exothermic (the heat of polymerization is 41 kcal/mol). 

The simplest way to catalyze the polymerization reaction that leads to an addition polymer is to add a source of a free radical to the monomer. The term free radical is used to describe a family of very reactive, short-lived components of a reaction that contain one or more unpaired electrons. In the presence of a free radical, addition polymers form by a chain-reaction mechanism that contains chain-initiation, chain-propagation, and chain- termination steps. 

Once this intermediate is formed, growth appears to be very rapid through addition of monomer units which condense near either radical site. High molecular weight polymers are then formed by a free radical addition mechanism. 

Surprise 62 addressed nucleophilic additions to fluorinated alkenes. Here, a free-radical addition is presented. What is the product of a reaction of methanol and 1-perfluorobutene in the presence of dibenzoyl peroxide ... 

In the case of a free-radical addition of hydrogen bromide, a type of addition limited to hydrogen bromide only, the attacking species is not proton, but a bromine atom that will join the carbon in such a way as to generate a more stable free-radical species. It will add to the carbon carrying two fluorines. In the intermediate free radical, the single electron is better accommodated at the carbon holding chlorine, because chlorine can disperse the electrons in its d-orbitals. 

Dowbenko (1964) has shown that carbon tetrachloride, chloroform and several other compounds react with a s-cis-l,5-cyclo-octadiene by a free-radical transannular 1,5-cyclo-addition to give derivatives of bicyclo-[3,3,0]octane. He suggested that the cyclo-addition may occur by a concerted reaction in which the configuration of the diene is such that the two double bonds lie in close proximity, or alternatively by a step-wise reaction which involves a free-radical addition across the ring. 

A free-radical addition reaction, the solvent-dependence of which has been studied in thirty-nine solvents, is the addition of the 4-(dimethylamino)benzenethiyl radical to a-methylstyrene cf. Eq. (5-72) [576]. 

Plasma-induced species act as initiator of polymerization. Polymerization characteristics and properties of polymers formed by plasma-induced polymerization strongly resemble those of the thermal polymerization of the corresponding monomer [2-12]. Results indicate that plasma-induced polymerization is a free radical addition polymerization initiated by difunctional free radicals created by plasma. The molecular weight of polymer increases with the polymerization time, which is distinctively different from the initiator-initiated free radical addition polymerization. 

Free radical polymerization offers a convenient approach toward the design and synthesis of special polymers for almost every area. In a free radical addition polymerization, the growing chain end bears an unpaired electron. A free radical is usually formed by the decomposition of a relatively unstable material called initiator. The free radical is capable of reacting to open the double bond of a vinyl monomer and add to it, with an electron remaining unpaired. The energy of activation for the propagation is 2-5 kcal/mol that indicates an extremely fast reaction (for condensation reaction this is 30 to 60 kcal/mol). Thus, in a very short time (usually a few seconds or less) many more monomers add successively... 

A highly efficient synthesis of geminally substituted dicyanocyclopropanes has been achieved by Boldt and coworkers using a free radical addition of bromodicyanomethane to aliphatic and cyclic alkenes under photolytic reaction conditions (equation 65) . The intermediate addition products, i.e. 2-bromoalkylmalononitriles (224), are easily isolated and can be transformed info the dicyanocyclopropanes by treatment with... 

The oxidation of substituted aromatic hydrocarbons by Mn(OAc)3 in refluxing acetic acid proceeds by two competing mechanisms (a) a free radical addition of carboxymethyl radical to the nuclear ring, forming 2-arylacetic acids and (b) a benzylic hydrogen abstraction by Mn resulting in the formation of benzyl acetates. " In the presence of strong acids such as sulfuric, trichloro- or trifluoro-acetic acids, only benzylic oxidation products are readily formed at room temperature (equation 207). ... 

The anti-Markovnikov addition of HBr to alkenes was probably the first free-radical addition reaction to be discovered. The discovery was inadvertent around the turn of the twentieth century, scientists studying the regiochemistry of addition of HBr to alkenes found that the proportion of Markovnikov to anti-Markovnikov addition products varied inexplicably from run to run. Eventually, it was discovered that impurities such as O2 and peroxides greatly increased the amount of anti-Markovnikov addition product. The results were later explained by a free-radical addition mechanism. The anti-Markovnikov regiochemistry derives from the addi-ton of the Br- radical to the less substituted C of the alkene (steric reasons) to give the lower energy, more substituted radical (electronic reasons). In a polar reaction, Br- would add to the more substituted C of the alkene. 

Addition of olefins. The work of Hassner et al. (1, 757) on addition of nitryl iodide to olefins has now been published.1 The reaction probably proceeds by a free-radical addition involving N02-. 

Previous study [18] on oxidation of thiols by transition metal oxide(s) in the presence of olefins resulted in the formation of corresponding sulphides indicating a free radical addition reaction in which metal oxide acts as an initiator for the production of thiyl radicals(RS-). The disulphide is formed by the dimerization of thiyl radieals (RS )- Based on this, a mechanism for thiol oxidation by manganese nodule (Only oxides of Mn, Fe, Co and Cu in manganese nodule are responsible for oxidation of thiols) is delineated as follows ... 

Allylarton. A free radical addition of A-bromoacetyloxazolidinones to branched allylsilanes with subsequent elimination effects homologation of the N-acyl group. Both the addition and the elimination steps are promoted by Yb(OTf)3-... 

Solution The information strongly points to a free-radical addition of chlorine to tetrachloroethylene. The fact that the reaction does not take place in the dark, forms many molecules of hexachloroethane with massive consumption of chlorine upon exposure to U.V., and is inhibited by the addition of oxygen can all be explained readily by a free-radical process. 

Poly(vinyl acetate) (PVA) and ethylene-vinyl acetate (EVA) copolymer adhesives have much in common, yet represent extremes in the degree of sophistication of their production processes. Both products are stable suspensions in water of a film-forming polymer, the particles of which are generally spherical. They are made by emulsion polymerization, which uses a free-radical addition mechanism to polymerize the monomer in the presence of water and stabilizers. Vinyl acetate is the sole or major monomeric raw material. 

Since emulsion polymerization is a free-radical addition polymerization, all the kinetic events, namely, initiation, propagation, termination and transfer reactions which have already been described in Chapter 1, are applicable to describe the overall rate of the polymerization and molar mass development of the latex polymer. However, the heterogeneous nature of the polymerization adds some complications due to partitioning of the various ingredients between the phases ... 

The first commercially feasible process for converting acrylic fibers to carbon fibers was developed by Walt, Phillips, and Johnson of the Royal Aircraft Establishment (RAE) in collaboration with the acrylic fiber producer, Courtaulds [621]. In the RAE process, the acrylic precursor is converted to carbon fiber in a two-step process [622]. Preoxidation or filament stabilization is carried out in the first stage. The precursor is heated in an oxygen atmosphere under tension at a temperature of approximately 200 250°C, well below its carbonizing temperature (approximately 800°C). At this temperature, the nitrile groups react with each other via a free radical addition process leading to the so-called ladder structure shown in reaction 12.34 [609,621 625]. 

Resin-modified glass-ionomers - these are similar to the above, but hardening also takes place by a free radical addition polymerization reaction, in addition to the acid-base reaction. 

Polyvinyl Chloride (PVC). Polyvinyl chloride polymers (PVC), generally referred to as vinyl resins, are prepared by the polymerization of vinyl chloride in a free radical addition polymerization reaction. Vinyl chloride monomer is prepared by reacting ethylene with chlorine to form 1,2-dichloroethane. The 1,2 dichloroethane is then cracked to give vinyl chloride. The polymerization reaction is depicted in Fig. 2.41. 

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