Reactions of amine oxides

Enamines can be obtained as the products of the Polonovski reaction of amine oxides and, in particular, by reaction of piperidine A -oxides with acetic anhydride. This is primarily due to the fact that when acetate is the counterion the intermediate iminium ions are labile and readily tautomerize. The formation of enamines during the Polonovski reaction is also favored by the presence of a base. In fact, enamines are often obtained in high yield from the reaction of an IV-oxide with trifluoroacetic anhydride in the presence of triethylamine or pyridine. Conversion of intermediate iminium ions, generated under modi-fred Polonovski conditions, to enamine products can also occur during hydrolytic work-up. 

Although in cyclic systems studied to date the N-oxide function has been for the most part incorporated into a six-membered ring system, there are several examples where pyrrolidine or dihydropyrrole A -oxides are the substrates. For instance, the reaction of amine oxide (55) with acetic anhydride at 0 C provides a convenient route to the 7V-alkylisoindole (56 equation 16). ... 

Edward, J. T., Whiting, J. Reactions of amine oxides and hydroxylamines with sulfur dioxide. Can. J. Chem. 1971, 49, 3502-3514. 

Part I. The Reactions of Amines Oxidation, Reduction, Addition, Substitution, and Rearrangement Part II. Some Organophosphorus Chemistry... 

A variety of substituted alkanolamines (Table 2) can also be made by reaction of oxide with the appropriate amine. Aminoethylethanolamine is made from the reaction of ethylenediamine [107-15-3J and ethylene oxide. Methyldiethanolamine is made from the reaction of ethylene oxide and methylamine [74-89-5J. Diethylethanolamine is made by the reaction of diethylamine [109-87-7] and ethylene oxide. 

Metal Catalysis. Aqueous solutions of amine oxides are unstable in the presence of mild steel and thermal decomposition to secondary amines and aldehydes under acidic conditions occurs (24,25). The reaction proceeds by a free-radical mechanism (26). The decomposition is also cataly2ed by V(III) and Cu(I). 

Analytical methods iaclude thin-layer chromatography (69), gas chromatography (70), and specific methods for determining amine oxides ia detergeats (71) and foods (72). Nuclear magnetic resonance (73—75) and mass spectrometry (76) have also been used. A frequentiy used procedure for iadustrial amine oxides (77) iavolves titratioa with hydrochloric acid before and after conversion of the amine to the quaternary ammonium salt by reaction with methyl iodide. A simple, rapid quaHty control procedure has been developed for the deterrniaation of amine oxide and unreacted tertiary amine (78). 

Ethylene oxide is a highly active intermediate. It reacts with all compounds that have a labile hydrogen such as water, alcohols, organic acids, and amines. The epoxide ring opens, and a new compound with a hydroxyethyl group is produced. The addition of a hydroxyethyl group increases the water solubility of the resulting compound. Eurther reaction of ethylene oxide produces polyethylene oxide derivatives with increased water solubility. 

Many of the reactions of amines are familiar from past chapters. Thus, amines react with alkyl halides in S 2 reactions and with acid chlorides in nucleophilic acyl substitution reactions. Amines also undergo E2 elimination to yield alkenes if they are first qualernized by treatment with iodomethane and then heated with silver oxide, a process called the Hofmann elimination. 

Dirheniumheptoxide 2154 is converted by TCS 14, in the presence of 2,2 -dipyri-dine, into the dipyridine complex 2160 [77]. Free ReCls, NbCls, and WCI5 react with HMDSO 7 and 2,2 -bipyridine to form bipyridine oxochloride complexes 2161 and TCS 14, with reversal of the hitherto described reactions of metal oxides with TCS 14. The analogous Mo complex 2162 undergoes silylahon-amination by N-trimethylsilyl-tert-butylamine 2163 to give the bis-imine complex 2164 and HMDSO 7 [77] (Scheme 13.22). 

Type I MCRs are usually reactions of amines, carbonyl compounds, and weak acids. Since all steps of the reaction are in equilibrium, the products are generally obtained in low purity and low yields. However, if one of the substrates is a bi-funchonal compound the primarily formed products can subsequently be transformed into, for example, heterocycles in an irreversible manner (type II MCRs). Because of this final irreversible step, the equilibrium is forced towards the product side. Such MCRs often give pure products in almost quantitative yields. Similarly, in MCRs employing isocyanides there is also an irreversible step, as the carbon of the isocyanide moiety is formally oxidized to CIV. In the case of type III MCRs, only a few examples are known in preparative organic chemistry, whereas in Nature the majority of biochemical compounds are formed by such transformations [3]. 

The decay of amine oxidized by hydroperoxide occurs much more rapidly than free radical generation. Apparently, these reactions proceed by chain mechanism. The diatomic phenols and aryldiamines (QH2) must react with ROOH by the chain mechanism in which the semiquinone radical -QH that reduces hydroperoxide plays the key role. The following chain mechanism can be supposed [122] ... 

Hence, the copper surface catalyzes the following reactions (a) decomposition of hydroperoxide to free radicals, (b) generation of free radicals by dioxygen, (c) reaction of hydroperoxide with amine, and (d) heterogeneous reaction of dioxygen with amine with free radical formation. All these reactions occur homolytically [13]. The products of amines oxidation additionally retard the oxidation of hydrocarbons after induction period. The kinetic characteristics of these reactions (T-6, T = 398 K, [13]) are presented below. 

In many instances it is not necessary to isolate the acetonitrile complex or to carry out the reaction in acetonitrile. The use of amine oxide as a means of displacing carbonyl groups in metal carbonyls is well documented, and reaction proceeds smoothly with the carbonyl in the presence of a variety of ligands—e.g., ethylene or pyridine—to yield the monosubstituted derivatives. The advantage of the acetonitrile adducts is the stability of the compounds and the reactivity of the amine oxide toward acidic ligands. 

Few studies have systematically examined how chemical characteristics of organic reductants influence rates of reductive dissolution. Oxidation of aliphatic alcohols and amines by iron, cobalt, and nickel oxide-coated electrodes was examined by Fleischman et al. (38). Experiments revealed that reductant molecules adsorb to the oxide surface, and that electron transfer within the surface complex is the rate-limiting step. It was also found that (i) amines are oxidized more quickly than corresponding alcohols, (ii) primary alcohols and amines are oxidized more quickly than secondary and tertiary analogs, and (iii) increased chain length and branching inhibit the reaction (38). The three different transition metal oxide surfaces exhibited different behavior as well. Rates of amine oxidation by the oxides considered decreased in the order Ni > Co >... 

While anodic amide oxidations have found the most synthetic use to date, the oxidation of nitrogen-containing molecules is not limited to amide substrates. A variety of amine oxidations have been studied, and the Kolbe electrolysis of carboxylic acids has been used to generate nitrogen-based reactive intermediates. Many of these reactions also offer unique synthetic advantages (Sects. 10.2 and 10.3). 

Another example is provided by the application of the modified Polonovski reaction to A3-piperideines. Treatment of amine oxides (141) with trifluoroacetic anhydride results in the formation of iminium ion (142). These compounds can behave as useful synthetic intermediates, reacting with a number of nucleophiles such as cyanide ion (80JA1064). 

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