Ozone amines, reactions with

Alkylaziridines can be stereospecifically deaminated to alkenes by reaction with m-chioroperbenzoic acid (70AG(E)374). The reaction and work-up are carried out in the dark to avoid isomerization of the cw-alkene, and the mechanism is thought to involve an initial oxidation to an amine oxide followed by a concerted elimination. Aziridine oxides have been generated by treating aziridines with ozone at low temperatures (71JA4082). Two... 

Nickel peroxide is a solid, insoluble oxidant prepared by reaction of nickel (II) salts with hypochlorite or ozone in aqueous alkaline solution. This reagent when used in nonpolar medium is similar to, but more reactive than, activated manganese dioxide in selectively oxidizing allylic or acetylenic alcohols. It also reacts rapidly with amines, phenols, hydrazones and sulfides so that selective oxidation of allylic alcohols in the presence of these functionalities may not be possible. In basic media the oxidizing power of nickel peroxide is increased and saturated primary alcohols can be oxidized directly to carboxylic acids. In the presence of ammonia at —20°, primary allylic alcohols give amides while at elevated temperatures nitriles are formed. At elevated temperatures efficient cleavage of a-glycols, a-ketols... 

TS-1 is a material that perfectly fits the definition of single-site catalyst discussed in the previous Section. It is an active and selective catalyst in a number of low-temperature oxidation reactions with aqueous H2O2 as the oxidant. Such reactions include phenol hydroxylation [9,17], olefin epoxida-tion [9,10,14,17,40], alkane oxidation [11,17,20], oxidation of ammonia to hydroxylamine [14,17,18], cyclohexanone ammoximation [8,17,18,41], conversion of secondary amines to dialkylhydroxylamines [8,17], and conversion of secondary alcohols to ketones [9,17], (see Fig. 1). Few oxidation reactions with ozone and oxygen as oxidants have been investigated. 

Kinetic Parameters of Phenols and Amines Reactions with Hydroperoxides, Dioxygen, Ozone, and Nitrogen Dioxide in IPM Model [4,110-114]... 

While primary aliphatic amines are converted to nitro compounds on reaction with ozone these reactions are accompanied by numerous by-products.Such side-reactions are largely suppressed by first dissolving the amine onto silica gel followed by passing a stream of 3 % ozone in oxygen through the solid at -78 °C under anhydrous conditions, where yields of between 60 and 70 % are reported. This route has been used to synthesize the energetic cyclopropane (65) from the diamine (64) (Table 1.7). ... 

Bound nitrogen includes all nitrogen-containing compounds, except N2, dissolved in water. Kjeldahl nitrogen analysis, described in Section 7-2, is excellent for amines and amides but fails to respond to many other forms of nitrogen. An automated combustion analyzer converts almost all forms of nitrogen in aqueous samples into NO, which is measured by chemiluminescence after reaction with ozone 17... 

The colloidal addition thus retards the catalytic activity of the platinum possibly by adsorption of the colloid by the platinum. W. Streeker and H. Thienemann observed that hydroxylamine hydrate radily reacts with ozone, forming hydroxyl-amine nitrate. The reaction is net complete and an excess of ozone is needed. 

Ozonium Ion (H03+). Ozone is a resonance hybrid of canonical structures 50a-50d.135 Ozone does in fact act as a 1,3-dipole—that is, either as an electrophile or a nucleophile. The electrophilic nature of ozone has been recognized for a long time in its reactions with alkenes, alkynes, arenes, amines, phosphines,... 

On the other hand, the indirect type of ozonation is due to the reactions of free radical species, especially the hydroxyl radical, with the organic matter present in water. These free radicals come from reaction mechanisms of ozone decomposition in water that can be initiated by the hydroxyl ion or, to be more precise, by the hydroperoxide ion as shown in reactions (4) and (5). Ozone reacts very selectively through direct reactions with compounds with specific functional groups in their molecules. Examples are unsaturated and aromatic hydrocarbons with substituents such as hydroxyl, methyl, amine groups, etc. [45,46],... 

The rate of reaction of ozone with amine was determined during the ozonization of rubber solution, where the reaction between ozone and rubber also proceeded concurrently. The extent of the reaction of rubber with ozone was calculated from the change in unsaturation of the rubber determined by the Wijs reagent. For example, SBR (Japan Synthetic Rubber, JSR 1502), purified by precipitation with acetone from benzene solution, was dissolved in carbon tetrachloride to give a 5% rubber solution. The rubber solution (20 ml.) was added with 80 ml. of carbon tetrachloride containing 1 X 10 3 mole of amine derivatives. Oxygen, containing 0.89% ozone, was introduced into the solution at 30°C. for 3 minutes at the rate of 550-560 ml./min. Under these conditions, all... 

After passage through the amine solution, any unreacted ozone was absorbed in 2% potassium iodide solution contained in a gas washing bottle. The volume of the ozonated oxygen, passed through the solution and stripped of ozone by the amine solution or potassium iodide solution, was measured with a wet-test meter. The reaction of ozone with tertiary amines was so rapid that at an ozone flow of 56 mg. per minute no excess ozone appeared in the potassium iodide trap during the reaction. The addition of ozone was stopped when the potassium iodide showed the yellow color due to iodine. 

Like 2-aminopyridines and 2-aminopyrimidine, 2-aminopyrazine (39) (Scheme 29) has been converted into the nitroso compound (121) by reaction with dimethyl sulfide and NCS followed by deprotonation of the resulting sulfonium salt with sodium methoxide to the 5, 5-dimethylsulfilimine and then oxidation with MCPBA <82JOC552>. The extremely reactive nitrosopyrazine (121) condenses with 1,3-dienes to give 3,6-dihydro-1,2-oxazines and with aromatic amines in the presence of acid to gives azo compounds, and is smoothly oxidized with ozone or sodium hypochlorite to 2-nitropyrazine (122). Methyl 3-aminopyrazinecarboxylate reacts with thiophosgene to produce the... 

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