Other Useful Radical Reactions

Silyl radicals (Si) obtained by reaction of 2 or 4 with thermally generated t-BuO radicals add readily to pyrazine and nitroalkanes to form the corresponding adducts 27 and 28 for which EPR spectra have been recorded [13]. 

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Without other alternatives, the carboxyalkyl radicals couple to form dibasic acids HOOC(CH)2 COOH. In addition, the carboxyalkyl radical can be used for other desired radical reactions, eg, hydrogen abstraction, vinyl monomer polymerization, addition of carbon monoxide, etc. The reactions of this radical with chloride and cyanide ions are used to produce amino acids and lactams employed in the manufacture of polyamides, eg, nylon. 

Another important rearrangement is that of cyclopropylmethyl radicals to the corresponding homoallyl radicals. This is an exceptionally fast reaction (t1/2 10 8) and has been used as a radical clock to determine the rates of other free-radical reactions.95 Cyclopropylcarbene also undergoes rearrangement, leading to cyclobutene.96... 

The mapping shown in Fig. 1 includes references to SBR and styrene block copolymers in the PB search. Removing these citations from the database reduced the number to 4297, which can be seen mapped in Fig. 3. the area of high activity is centered on hydroxy terminated PB (HTPB). Low-Mn HTPB can be prepared by a variety of polymerization processes such as radical, anionic, or even using acyclic diene metathesis (ADMET).f The HTPB has a variety of uses as a propellant. " Other uses include reaction with epoxy resins, nylon, urethane, or even in the formulation of adhesives.t" The use of HTPB as an oxygen scavenger in polyamide, polyvinyl alcohol, and multilayer... 

The HAS reaction proceeds via a sigma (a) complex (1) with substitution being completed by the loss of the leaving group Y, which is usually hydrogen (Scheme 9.1, Y = H). Examples where the cyclohexadienyl radicals become trapped by fast reductants to form cyclohexadiene [2] and the detection of radical intermediates by ESR or CIDNP provide evidence that the cyclohexadienyl radicals are intermediates in this reaction [3]. In some systems, the addition of a radical onto the arene is the rate-determining step, because of the loss of aromaticity. For example, the rate constant for the addition of the ferf-butyl radical to benzene at 79°C is 3.8 x 10 M s [4], which is clearly at the lower end of a useful radical reaction. The arene needs to be used at high concentration, or as the solvent, in order to compensate for poor rates. On the other hand, as the rate of addition of the phenyl radical to benzene is 4.5 x 10 s" [5], it is more useful in these kind of reactions. 

Structopendant unsaturated polyesters, containing double bonds within the polymer chain, are produced by step-growth polycondensation reaction of an unsaturated diacid or anhydride, such as fumaric add or maleic anhydride, with a diol. Structural unsymmetry in the diol component lowers the viscosity of the prepolymer. Mostly, crosslinking of the structopendant unsaturated polyester is accomplished by copolymerization with alkene monomers such as styrene, methyl methacrylate, or others using radical initiators. 

In addition to the selective oxidation reactions above, a number of other free-radical reactions are summarized herein. Tanko and Blackert (267,268) report the free-radical side-chain bromination of toluene and ethylbenzene in SCCO2 using bromide radicals initiated photochemically from molecular bromine. They report the production of the corresponding benzylic bromides in high yield with selectivities essentially identical to that observed in a conventional chlorinated... 

Other nonpolymeric radical-initiated processes include oxidation, autoxidation of hydrocarbons, chlorination, bromination, and other additions to double bonds. The same types of initiators are generally used for initiating polymerization and nonpolymerization reactions. Radical reactions are extensively discussed in the chemical Hterature (3—15). 

Nitrations are highly exothermic, ie, ca 126 kj/mol (30 kcal/mol). However, the heat of reaction varies with the hydrocarbon that is nitrated. The mechanism of a nitration depends on the reactants and the operating conditions. The reactions usually are either ionic or free-radical. Ionic nitrations are commonly used for aromatics many heterocycHcs hydroxyl compounds, eg, simple alcohols, glycols, glycerol, and cellulose and amines. Nitration of paraffins, cycloparaffins, and olefins frequentiy involves a free-radical reaction. Aromatic compounds and other hydrocarbons sometimes can be nitrated by free-radical reactions, but generally such reactions are less successful. 

This synthesis method can be utilised by any alkene or alkyne, but steric hindrance on internal double bonds can cause these reactions to be quite slow. Conjugated dienes and aromatic alkenes are not suited for the ultraviolet light-initiated process. The use of other free-radical initiators is required in free-radical-initiated reactions involving these species. 

Pyrolysis. Pyrolysis of 1,2-dichloroethane in the temperature range of 340—515°C gives vinyl chloride, hydrogen chloride, and traces of acetylene (1,18) and 2-chlorobutadiene. Reaction rate is accelerated by chlorine (19), bromine, bromotrichloromethane, carbon tetrachloride (20), and other free-radical generators. Catalytic dehydrochlorination of 1,2-dichloroethane on activated alumina (3), metal carbonate, and sulfate salts (5) has been reported, and lasers have been used to initiate the cracking reaction, although not at a low enough temperature to show economic benefits. 

Dichloroethane is produced by the vapor- (28) or Hquid-phase chlorination of ethylene. Most Hquid-phase processes use small amounts of ferric chloride as the catalyst. Other catalysts claimed in the patent Hterature include aluminum chloride, antimony pentachloride, and cupric chloride and an ammonium, alkaU, or alkaline-earth tetrachloroferrate (29). The chlorination is carried out at 40—50°C with 5% air or other free-radical inhibitors (30) added to prevent substitution chlorination of the product. Selectivities under these conditions are nearly stoichiometric to the desired product. The exothermic heat of reaction vapori2es the 1,2-dichloroethane product, which is purified by distillation. 

The refined grade s fastest growing use is as a commercial extraction solvent and reaction medium. Other uses are as a solvent for radical-free copolymerization of maleic anhydride and an alkyl vinyl ether, and as a solvent for the polymerization of butadiene and isoprene usiag lithium alkyls as catalyst. Other laboratory appHcations include use as a solvent for Grignard reagents, and also for phase-transfer catalysts. 

A radical reaction is sometimes observed to compete with the particularly slow acid hydrolyses of diaziridines derived from formaldehyde. With other diaziridines the radical reaction can be made to predominate by using HCl in carbon tetrachloride solution. Acetaldehyde, butyraldehyde, butylamine and ammonia are obtained from (160) (64CB49). 

The first three chapters discuss fundamental bonding theory, stereochemistry, and conformation, respectively. Chapter 4 discusses the means of study and description of reaction mechanisms. Chapter 9 focuses on aromaticity and aromatic stabilization and can be used at an earlier stage of a course if an instructor desires to do so. The other chapters discuss specific mechanistic types, including nucleophilic substitution, polar additions and eliminations, carbon acids and enolates, carbonyl chemistry, aromatic substitution, concerted reactions, free-radical reactions, and photochemistry. 

Historically, ethylene potymerization was carried out at high pressure (1000-3000 atm) and high temperature (100-250 °C) in the presence of a catalyst such as benzoyl peroxide, although other catalysts and reaction conditions are now more often used. The key step is the addition of a radical to the ethylene double bond, a reaction similar in many respects to what takes place in the addition of an electrophile. In writing the mechanism, recall that a curved half-arrow, or "fishhook" A, is used to show the movement of a single electron, as opposed to the full curved arrow used to show the movement of an electron pair in a polar reaction. 

The most popular methods are the Q-e (Section 7.3.4.1) and Patterns of Reactivity schemes (Section 7.3.4.2). Both methods may also be used to predict transfer constants (Section 6.2.1). For furtherdiscussionontheapplicationofthe.se and other methods to predict rate constants in radical reactions, see Section 2.3.7. 

Diacyl peroxides undergo thermal and photochemical decomposition to give radical intermediates (for a recent review, see Hiatt, 1971). Mechanistically the reactions are well understood as a result of the many investigations of products and kinetics of thermal decomposition (reviewed by DeTar, 1967 Cubbon, 1970). Not surprisingly, therefore, one of the earliest reports of CIDNP concerned the thermal decomposition of benzoyl peroxide (Bargon et al., 1967 Bargon and Fischer, 1967) and peroxide decompositions have been used more widely than any other class of reaction in testing theories of the phenomenon. 

The majority of sequential radical reactions deal with cyclizations as the key steps. The constructions of carbocycles, oxygen, and nitrogen heterocycles using (TMSlsSiH as a mediator are many and represents the expansion and importance of these synthetic approaches. For example, Nicolaou and coworkers found that (TMSlsSiH serves as a superior reagent in the radical-based approach toward the synthesis of azadirachtin, an antifeedant agent currently used as an insecticide, and in other related systems. ° ° Here below we collected a number of reactions mostly from the recent work in the area of intramolecular reactions. 

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