Oxygen of amines

The participation of the singlet states of dyes such as rose bengal (RB, tetraiodotetrachlorofluorescein, sodium salt) and MB during the sensitized oxygenation of amines was demonstrated by Davidson (40). Fluorescence quenching Stem-Volmer constants were reported for several amines, halide anions, and for 3-carotene and were consistent with charge transfer stabilization of an exciplex quenching intermediate. 

A networked supramolecular POM-based hybrid catalyst has been synthesized by Ikegami and coworkers via the self-assembly of [PWi2O40]3 and non-crosslinked copolymer based on N-isopropylacrylamide (NIPAM) and ammonium cations (Figure 6.7) [124, 125]. This heterogeneous NIPAM-POM hybrid catalyst showed very high catalytic activity for the epoxidation of allylic alcohols with H202 (e.g., up to 35 000 TON for phytol). In addition, the oxygenation of amines and sulfide could be... 

Oxygenation of amines and secondary alcokois. RuCla (hydrated) catalyzes the oxygenation of primary and secondary amines and secondary alcohols in toluene (100°). Addition of water inhibits formation of alkenes in the case of alcohols. 

Cu(py)3(C6HsN 0)], in one instance [170]. Since there is at least a possibility that catalytic oxygen activation may be occurring and since we have been concerned with copper-amine complexes as catalysts for oxygenations of amines and other organic substrates, consideration of this reaction seems warranted here. 

The physical properties of amine oxides are attributed to the semipolar or coordinate bond between the oxygen and nitrogen atoms with high electron density residing on oxygen. 

Oxygen-Cont iiningAmines. This group includes amine oxides, ethoxylated alkylamines, l-(2-hydroxyethyl)-2-imidazolines, and alkoxylates of ethylenediamine. Oxygen-containing amines are steadily increasing in economic importance. 

Oxaziridines are generally formed by the action of a peracid on a combination of a carbonyl compound and an amine, either as a Schiff base (243) or a simple mixture. Yields are between 65 and 90%. Although oxygenation of Schiff bases is formally analogous to epoxidation of alkenes, the true mechanism is still under discussion. More favored than an epoxidation-type mechanism is formation of a condensation product (244), from which an acyloxy group is displaced with formation of an O—N bond. 

Enby 6 is an example of a stereospecific elimination reaction of an alkyl halide in which the transition state requires die proton and bromide ion that are lost to be in an anti orientation with respect to each odier. The diastereomeric threo- and e/ytAra-l-bromo-1,2-diphenyl-propanes undergo )3-elimination to produce stereoisomeric products. Enby 7 is an example of a pyrolytic elimination requiring a syn orientation of die proton that is removed and the nitrogen atom of the amine oxide group. The elimination proceeds through a cyclic transition state in which the proton is transferred to die oxygen of die amine oxide group. 

Similarly the active oxygen of oxaziranes can be transferred to triphenylphosphine with the formation of ]ihosphine oxide and to tertiary amines yielding amine oxides. ... 

As feed systems usually contain copper alloys, the use of amines for their protection may seem somewhat strange as copper is prone to attack in ammonia/carbon dioxide/oxygen environments, with the formation of complex cupric or cuprous compounds. The requisite degree of protection can be achieved, however, by maintaining the concentrations strictly within the acceptable target range. 

Hoesch reaction. In most cases, a Lewis acid is necessary zinc chloride is the most common. The reaction is generally useful only with phenols, phenolic ethers, and some reactive heterocyclic compounds (e.g., pyrrole), but it can be extended to aromatic amines by the use of BCls. Acylation in the case of amines is regioselectively ortho. Monohydric phenols, however, generally do not give ketones " but are attacked at the oxygen to produce imino esters. Many nitriles... 

In an attempt to design the p-turn-peptide-mimics, aspartic acid (an amino acid also known as aspartate) and lysine (an amino acid especially found in gelatin and casein) were attached to each amine group of 1,3-diaminoada-mantane in the form of amide bonds. The term p-turn refers to a peptide chain that forms a tight loop such that the carbonyl oxygen of one residue is hydrogen... 

The oxidation of N, A-dimethylaniline by aerated, ethanolic cupric chloride to give a mixture of products including methyl and crystal violets is simple second-order when an excess of amine is used Presumably Cu(I) is re-oxidised by dissolved oxygen, for otherwise the observed linearity of log [residual amine] versus time plots would not be found as Cu(II) disappears. Under nitrogen the kinetics are complex, but a new optical absorption (472 and 1007 nm) appears immediately on mixing the reactants. This absorption decays whilst a new one at 740 nm develops. The latter absorption originates from a 1 1 complex formulated... 

Catechin-immobilizing polymer particles were prepared by laccase-catalyzed oxidation of catechin in the presence of amine-containing porous polymer particles. The resulting particles showed good scavenging activity toward stable free l,l-diphenyl-2-picryl-hydrazyl radical and 2,2 -azinobis(3-ethylbenzothiazoline-6-sulfonate) radical cation. These particles may be applied for packed column systems to remove radical species such as reactive oxygen closely related to various diseases. 

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