Amine oxidation potential

As with arene-amine radical ion pairs, the ion pairs formed between ketones and amines can also suffer a-deprotona-tion. When triplet benzophenone is intercepted by amino acids, the aminium cation radical can be detected at acidic pH, but only the radical formed by aminium deprotonation is detectable in base (178). In the interaction of thioxanthone with trialky lamines, the triplet quenching rate constant correlates with amine oxidation potential, implicating rate determining radical ion pair formation which can also be observed spectroscopically. That the efficiency of electron exchange controls the overall reaction efficiency is consistent with the absence of an appreciable isotope effect when t-butylamine is used as an electron donor (179). 

J.K. Cha et al. developed a stereocontrolled synthesis of bicyclo[5.3.0]decan-3-ones from readily available acyclic substrates. Acyclic olefin-tethered amides were first subjected to the intramolecular Kulinkovich reaction to prepare bicyclic aminocyclopropanes. This was followed by a tandem ring-expansion-cyclization sequence triggered by aerobic oxidation. The reactive intermediates in this tandem process were aminium radicals (radical cations). The p-anisidine group was chosen to lower the amine oxidation potential. This substituent was crucial for the generation of the aminium radical (if Ar = phenyl, the ring aerobic oxidation is not feasible). 

Yasuda and Pac and their co-workers " have significantly extended the scope of ET-sensitized addition in their studies of the photoamination reactions of arenes and aryl olefins (Scheme 2). DCNB is a powerful electron acceptor (Table 1) capable of oxidizing the singlet slates of most arenes and aryl olefins (Table 2). Benzene does not undergo photoamination however a di-methoxy derivative and biphenyl are reactive. Photoamination products are generally obtained in high preparative yield using ammonia or primary amines however, secondary amines can only be used successfully with arenes such as anthracene which have oxidation potentials lower than those of secondary amines. When the amine oxidation potential is comparable to... 

The cellulose dissolving potential of the amine oxide family was first realized (79) in 1939, but it was not until 1969 that Eastman Kodak described the use of cycHc mono(/V-methy1amine-/V-oxide) compounds, eg, /V-methylmorpho1ine-/V-oxide [7529-22-8] (NMMO), as a solvent size for strengthening paper (80) by partially dissolving the cellulose fibers. 

Other patents (81,82) coveted the preparation of cellulose solutions using NMMO and speculated about their use as dialysis membranes, food casings (sausage skins), fibers, films, paper coatings, and nonwoven binders. NMMO emerged as the best of the amine oxides, and its commercial potential was demonstrated by American Enka (83,84). Others (85) have studied the cellulose-NMMO system in depth one paper indicates that further strength increases can be obtained by adding ammonium chloride or calcium chloride to the dope (86). 

Many different types of foaming agents are used, but nonionic surfactants are the most common, eg, ethoxylated fatty alcohols, fatty acid alkanolamides, fatty amine oxides, nonylphenol ethoxylates, and octylphenol ethoxylates, to name a few (see Alkylphenols). Anionic surfactants can be used, but with caution, due to potential complexing with cationic polymers commonly used in mousses. 

The performance potential of synergistic mixtures of anionics (e.g., alkanesulfonates) and amine oxides with hydroxyethylene groups was already analyzed some years ago [89]. It was shown that lauryldi(hydroxyethylene)amine N-oxide lowers the Zein values of the mixtures with alkanesulfonates. 

The sulfated alkylbenzenesulfonamides (no. 7-8) and alkylaroylsulfo-propionates (no. 9) were found to be efficient lime soap dispersants [27]. Although the nonionics (nos. 10-11) had low LSDR values they did not potentiate the detergency of soap and exhibited some antagonism. Amphoteric surfactants with alkyl side chains from C12 to C18 (nos. 12-13) possessed the lowest LSDR values, ranging from 2 to 4. The amine oxide derived from an aromatic sulfonamide had a low LSDR of 5 close to that of amphoterics. 

One of the most prominent characteristics of Fe(+2) is its ability to undergo oxidation leading to Fe(+3). This was used by Uchiyama et al. when they reported on Fe(+2)-ate complexes as potent electron transfer catalysts [7, 8]. These ferrates are accessible from FeCl2 and 3 equiv. of MeLi. The Fe(+2/+3) oxidation potential of [Me3Fe(+2)]Li 19 in THF is —2.50 V, thus being in between those of Sml2 (—2.33 V) and Mg (—3.05 V). With these alkyliron-ate complexes it was possible to realize a reductive desulfonylation of various A -sulfonylated amines 20 with different basicity. By using Mg metal to restore the active Fe(+2) species 19 a catalytic reductive desulfonylation process was achieved (Scheme 4). 

Table 5. Oxidation potentials (half peak potentials, Epl/2) of fluoro-ethylamines and related amines...

The electrooxidation of organosilicon compounds containing heteroatoms has been investigated extensively and various synthetic applications have been developed. Cooper and Owen studied the oxidation potentials of a series of silyl-substituted amines, phosphines, and sulfides, and observed that silyl substitution at the carbon adjacent to the heteroatom caused a significant decrease in the oxidation potentials (Table 4) [35]. 

The electrochemical behaviour of silyl-substituted nitrogen compounds is also interesting. The introduction of a silyl group at the carbon adjacent to the nitrogen of carbamates causes a significant decrease in the oxidation potentials, although such effect is much smaller for amines. Preparative electrochemical oxidation of silyl-substituted carbamates in methanol results in smooth and selective cleavage of the C Si bond and introduction of methanol at the a-... 

Since amines generally have low oxidation potentials, they are good electron donors in their ground state, and the donor ability is further enhanced by photoexcitation. The chemical consequence of this single electron transfer (SET) is the generation of the amine radical cations (aminium radicals) and an earlier review on the aminium radicals is available1. 

In the DCA-sensitized reaction of silyl amino esters 46 (equation 16) the formation of pyrrolidines 48 must be obtained through a desilylmethylation. This process can be prevented by attaching an electron-withdrawing group to the amine that obviously reduces its oxidation potential (equation 17)48. 

The oxidation of an amine can benefit from the use of an electroauxiliary [19-28]. Electroauxiliaries are substituents that both lower the initial oxidation potential of the substrate and control the formation of the subsequent reactive intermediates. To this end, the anodic oxidation of the 6-membered ring a-silylamines in the presence of cyanide was shown to afford a net displacement of the silyl... 

An electroreductive Barbier-type allyla-tion of imines (434) with allyl bromide (429) also occurs inaTHF-PbBr2/Bu4NBr-(Al/Pt) system to give homoallyl amine (436) (Scheme 151) [533]. The combination of Pb(II)/Pb(0) redox and a sacrificial metal anode in the electrolysis system plays a role as a mediator for both cathodic and anodic electron-transfer processes. The metals used in the anode must have a less positive anodic dissolution potential than the oxidation potentials of the organic materials in order to be present or to be formed in situ. In addition, the metal ion plays the role of a Lewis acid to form the iminium ion (437) by associating with imine (435) (Scheme 151). 

The polymers can be oxidized by differential pulse polarography. Their oxidation is metal-centered and leads to Ru(III) compounds. The potential is located aroimd -1-1.26 V (SCE). It can be stated that the polymers which contain the triphenylamine structure imits in the main chain show, as expected, an additional peak caused by the amine nitrogen. Substitution at the triphenylamine by electron-donating substituents lowers these potentials to 1.05 V (25), whereas acceptor substituents cause an increase of the oxidation potential (23). 

Azo and azoxy compounds are potential by-products of peroxyacetic acid oxidations, particularly when the rate of oxidation is slow. Competitive condensation reactions are usually avoided by using an excess of oxidant and also avoiding the presence of excess acid which retards amine oxidation. The latter is sometimes suppressed by using a sodium bicarbonate buffer.i i i ... 

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. 

A similar pattern of reactivity has been observed by Burrows and coworkers for the reaction between A -acetyllysine methyl ester (Lys) and dG. This reaction was studied in order to gain an understanding of structural aspects of DNA-protein cross-links (DPCs). These cross-links are regarded as a common lesion of oxidative damage to cells, but remain, from a chemical point, a poorly understood DNA lesion. As pointed out by Burrows, oxidation of protein-DNA complexes should occur preferentially at the primary amines since these sites have a lower oxidation potential (1.1 V vs. NHE, pH 10) than G. While protonation of the primary amine inhibits the oxidative process, transient deprotonation of a lysine residue would give rise to a lysine aminyl radical (or aminium radical cation). Using... 

Monolayer properties of octadecyldimethylamine oxide alone and in combination wth sodium alkyl sulfate on aqueous substrate have been investigated. Nonionised amine oxide produces more expanded film than the ionised species minimum film expansion and highest surface potential are obtained at half ionisation. 

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