Free-radical coupling reactions

Didehydroferulic Acid 23 Formation. It should be noted that no direct evidence has ever been obtained in vivo to prove that didehydroferulic acid 23 is formed via free radical coupling reactions. This mechanism is assumed, since in vitro incubation of ferulic acid 1 and wheat pentosan, with... 

Aromatic Ring Cleavage of Phenolic 0-0-4 Substructure Model Compounds by Laccase. When vanillyl alcohol was used as a substrate, only biphenyl formation (C5-C5 linked) occurred and no evidence for the formation of any ring-opened products was obtained (26). Hence, we also examined the effect of laccase on the sterically hindered 4,6-di-<-butylguaiacol substrate 50, as it would be unlikely to undergo such free-radical coupling reactions... 

Thus, peroxidases may potentially effect direct free radical coupling reactions between aniline and humic substances or create additional substrate sites within the fiilvic or humic acid molecules for nucleophilic addition by aniline. A model for the latter pathway can be found in the work with guaiacol and 4-chloroaniline by Simmons et al. (19). Peroxidase catalyzed the coupling of guaiacol, itself not a substrate for nucleophilic addition, into the extended quinonoid dimer which subsequently underwent nucleophilic attack by the chloroaniline ... 

In the purest sense, lignin is a complex racemic consisting from aromatic heteropolymers produced by free radical coupling reactions initiated by enzymatic dehydrogenation of the three primary precursors, the hydroxycinnamyl alcohol monomers differing in their degree of methoxylation trans-4-coumaryl alcohol [3-(4-hydroxyphenyl)-2-propenol)], trans-coniferyl alcohol [3-(4-hydroxy-3-methoxyphenyl)-2-propenol)] and trans-sinapyl alcohols [3-(4-hydroxy-3,5-dime-thoxyphenyl)-2-propenol)] (Fig. 8.4). 

In case of the Cu(Tpzb) complex (5), formation of /u.- j j -peroxo dicopper(II) complex (1) from 11 was confirmed imder dioxygen (89) in both toluene and THF. For the Cu(L ) complex as well as the Cu(L = ) and Cu(L" ") complexes (6), it was reported that 11 afforded complex 1 in nonpolar solvents such as toluene (97). 1 reacts with phenols to regenerate 2 (98) and hydrogen peroxide (99). Hence, this catalytic system would allow only the regioselective coupling process from 2 and/or 3 and completely exclude free-radical coupling reactions the present reaction is thus recognized as radical-controlled oxidative polymerization. 

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. 

The above reactions proceed via free radical coupling. An alternative system for photochemically driven hydrocarbon functionalization evidently proceeds via the carbanion, which is obtained from reduction of the initially formed free radical3. The carbanion reacts with acetonitrile to give, after in situ hydrolysis, the methyl ketone, e.g., formation of (tricyclo[3.3.1.13-7]dec-1-yl)ethanone6. 

Bipyridyl (20) (63AHC(2)179) is synthesized by oxidative dimerization of pyridine over hot Raney nickel, while 4,4 -bipyridyl (21) (B-79MI10705) is made by free radical coupling of the pyridine radical anion generated by sodium in liquid ammonia, followed by air oxidation (Scheme 6). Quaternization of (21) with methyl chloride gives paraquat while reaction of (20) with 1,2-dibromoethane gives diquat. 

Redistribution is a free-radical chain reaction that does not consume oxygen or change the overall degree of polymerization. However, the net result of redistribution between polymeric phenols to form a monomeric phenol or phenoxy radical, followed by coupling of the monomer as in reaction (5) is the same as if two polymer molecules combined in a single step. 

Homopolymer PS and block copolymer poly(tert-butyl acrylate)-b-styrene, prepared by nitroxide-mediated living free-radical polymerization, were utilized for the functionalization of shortened SWCNTs through a radical coupling reaction (Scheme 1.33) [194]. 

Soluble Co compounds are generally employed in the autoxidation of hydrocarbons, i.e., the oxidation with O2 as the oxidant. In neat hydrocarbons, low concentrations of Co compounds accelerate the autoxidation since the Co2+/Co3+ couple is excellent for decomposing alkyl hydroperoxides and thus initiates free radical chain reactions. However, at high conversions, the Co may be deactivated by formation of insoluble clusters with side products of the hydrocarbon autoxidation. Moreover, high concentrations of a Co compound may actually inhibit the reaction because Co also terminates radical chains by reaction with ROO radicals ... 

These condensations, like the oxidative coupling of phenols, presumably are free radical chain reactions with aryloxy radicals as intermediates, but the gross features of the two types of reactions are quite different. At low extents of oxidation the oxidative coupling reaction... 

Radical cage effect and coupling (recombination) Radical coupling reactions do not dominate free radical chemistry as most radicals have very short lifetimes and are present in very low concentrations. Consequently, if short-lived radicals are to contribute to useful synthetic procedures by way of a radical coupling, all the events leading up to the coupling must take place in a solvent cage. 

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