Phenols, reaction with metal complexes

Considerable effort has been devoted to the development of enantiocatalytic MBH reactions, either with purely organic catalysts, or with metal complexes. Paradoxically, metal complex-mediated reactions were usually found to be more efficient in terms of enantioselectivity, reaction rates and scope of the substrates, than their organocatalytic counterparts [36, 56]. However, this picture is actually changing, and during the past few years the considerable advances made in organocatalytic MBH reactions have allowed the use of viable alternatives to the metal complex-mediated reactions. Today, most of the organocatalysts developed are bifunctional catalysts in which the chiral N- and P-based Lewis base is tethered with a Bronsted acid, such as (thio)urea and phenol derivatives. Alternatively, these acid co-catalysts can be used as additives with the nucleophile base. 

Phenol oxidations by metal complexes employ the (a- /2 2-peroxo)dicopper(II) and bis(u-oxo)-dicopper(III) complexes shown in Table 17.1(e) and (f), respectively as the oxidants [75]. In this study, the rate of phenol oxidation was correlated with phenol oxidation potential (Pqx)- We note that the use of the oxidation potential is more appropriate than the lEs of Figs. 17.7 and 17.8, since the latter approximates a gas phase internal energy for oxidation whereas the oxidation potential is the free energy for the solution reaction. Reaction of the substrates shown in Table... 

A transformation showing enhancement of the reactivity of phenol through transition metal complexation occurs in the reaction of [Os(NH3)s(fi -phenol]-(OTO2 with maleic anhydride in acetonitrile over 20 hours at ambient temperature followed by recovery of the product, dimethyl (4-hydroxyphenyl)succinate in 85% yield by simple ethereal precipitation and removal of the osmium by refluxing in acidic methanol (ref.39). These last two examples illustrate the versatility of the appropriately modified phenolic structure to function either in a nucleophilic or in an electrophilic manner. 

Irg 1076, AO-3 (CB), are used in combination with metal dithiolates, e.g., NiDEC, AO-30 (PD), due to the sensitized photoxidation of dithiolates by the oxidation products of phenols, particularly stilbenequinones (SQ, see reaction 9C) (Table 3). Hindered piperidines exhibit a complex behavior when present in combination with other antioxidants and stabilizers they have to be oxidized initially to the corresponding nitroxyl radical before becoming effective. Consequently, both CB-D and PD antioxidants, which remove alkyl peroxyl radicals and hydroperoxides, respectively, antagonise the UV stabilizing action of this class of compounds (e.g.. Table 3, NiDEC 4- Tin 770). However, since the hindered piperidines themselves are neither melt- nor heat-stabilizers for polymers, they have to be used with conventional antioxidants and stabilizers. 

Attempts have been made to catalyze the arrangement of 3-oxaquadricyclane to oxepins with transition-metal complexes.1 32 1 35 When dimethyl 2,4-dimethyl-3-oxaquadricyclane-l,5-dicarboxylate is treated with bis(benzonitrile)dichloroplatinum(II) or dicarbonylrhodium chloride dimer, an oxepin with a substitution pattern different from that following thermolysis is obtained as the main product. Instead of dimethyl 2,7-dimethyloxepin-4,5-dicarboxylate, the product of the thermal isomerization, dimethyl 2,5-dimethyloxepin-3,4-dicarboxylate (12), is formed due to the cleavage of a C O bond. This transition metal catalyzed cleavage accounts also for the formation of a 6-hydroxyfulvene [(cyclopentadienylidene)methanol] derivative (10-15%) and a substituted phenol (2-6%) as minor products.135 The proportion of reaction products is dependent on solvent, catalyst, and temperature. 

Metal complexes, dialkyl thiophosphates and dialkyl thiocarbamates of Zn, Ni, Ba, and Ca, in particular, are widely used for the stabilization of lubricants [30-32,34]. At moderate temperatures (350 400 K), these inhibitors are less efficient than phenols, but they are more potent at higher temperatures (430 480 K). The sophisticated mechanism of action of these antioxidants involves their reactions with hydroperoxide. The interaction of hydroperoxide with metal dialkyl thiophosphates induces a cascade of reactions [5,66-69],... 

Among the most important indirect methods of analysis which employ redox reactions are the bromination procedures for the determination of aromatic amines, phenols, and other compounds which undergo stoichiometric bromine substitution or addition. Bromine may be liberated quantitatively by the acidification of a bromate-bromide solution mixed with the sample. The excess, unreacted bromine can then be determined by reaction with iodide ions to liberate iodine, followed by titration of the iodine with sodium thiosulphate. An interesting extension of the bromination method employs 8-hydroxyquinoline (oxine) to effect a separation of a metal by solvent extraction or precipitation. The metal-oxine complex can then be determined by bromine substitution. 

Amines such as diethylamine, morpholine, pyridine, and /V, /V, /V, /V -tetramethylethylene-diamine are used to solubilize the metal salt and increase the pH of the reaction system so as to lower the oxidation potential of the phenol reactant. The polymerization does not proceed if one uses an amine that forms an insoluble metal complex. Some copper-amine catalysts are inactivated by hydrolysis via the water formed as a by-product of polymerization. The presence of a desiccant such as anhydrous magnesium sulfate or 4-A molecular sieve in the reaction mixture prevents this inactivation. Polymerization is terminated by sweeping the reaction system with nitrogen and the catalyst is inactivated and removed by using an aqueous chelating agent. 

The preparation of metal dithiophosphate complexes usually involves the reaction of metal halides or acetates with dithiophosphoric acids or their salts. The metal complexes are generally purified by repeated fractional crystallization from halocarbon solvents such as chloroform. The reactions of mixtures of alcohols and alcohols and phenols with phosphorus(V) sulfide allegedly,... 

In others, a transition metal catalyst may play the role. The over-all reactions are often complex, but with suitable control they may yield interesting products, as in the oxidative polymerization of 2,6-dimethyl-phenol (9). 

Because of the small concentration of the 2 1 complex the last term can be ignored. From the extreme rate values in the absence of zinc and with an excess of zinc, 2i and 22 are determined as 2.4 X 104 min.-1 and 1.57 min.-1 respectively. These values can be combined with the trend in the rate constants to give the stability constant of the reactive complex, presumably Zn(OR)(OAc), as 3 X 107. For the simple zinc complex in water the literature values of the stability constant for the 1 1 complex vary from 2.5 X 108 to 6.3 X 108. The diazo coupling reaction of the complex indicates the smaller effect of coordination vis a vis protonation since this reaction is very sensitive to such effects and does not proceed with phenols. Unfortunately the choice of cations for such a reaction is restricted since the cation should not interfere with the analytical methods used to obtain the kinetic data nor should it introduce additional reactions such as occur with transition metal cations which can catalyze the decomposition of the diazonium salt via a redox process. 

General Order of Rate Constants. The rate constants of electrophilic reactions of aromatic ligands and their metal complexes fall in the order fo, > kML > kffL. The difference between these rate constants becomes greater as the activity of the attacking reagent decreases. When L is a phenolate, HL is the phenol when L is an amine, HL is the corresponding ammonium derivative. The possible synthetic applications of this sequence can be appreciated from the fact that 8-hydroxyquinoline is usually sulfonated with 15 to 30% oleum, while its copper (II) complex can be readily sulfonated in 70% sulfuric add (5). 

Although hydroxyl radical is commonly assumed to be the most toxic of the oxygen radicals (with little direct evidence), other direct reactions are more likely to be important for understanding the cytotoxicity of peroxynitrite. A second oxidative pathway involves the heterolytic cleavage of peroxynitrite to form a nitronium-like species (N02 ), which is catalyzed hy transition metals (Beckman et al., 1992). Low molecular weight metal complexes as well as metals bound in superoxide dismutase and other proteins catalyze the nitration of a wide range of phenolics, including tyrosine residues in most proteins (Beckman et al., 1992). 

The catalytic activity of the metal complex on the oxidative reaction in solution is much influenced not only by the species and the structure of the complexes but also by the chemical environment around them. For instance, in the oxidative polymerization of phenols catalyzed by a Cu complex, the reaction rate varied about 102 times with changes in the composition of the solvent, and the highest rate was observed for polymerization in a benzene solvent162. Thus, we used the copolymer of styrene and 4-vinylpyridine(PSP) as the polymer ligand and studied the effect on the catalysis of the non-polar field formed by the polymer ligand163. ... 

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