Aliphatic amines peroxide

Unsymmetrical secondary aliphatic amines have been prepared by reaction of alkyl halides with benzylidene amines and subsequent hydrolysis 814 by reaction of alkyl halides with alkyl amines 5 by reduction of amine-aldehyde adducts 8-8 and by dealkylation of tertiary amines with dibenzoyl peroxide. ... 

Primary aliphatic or aromatic amines RNH2 are converted into carbamates RNHCC Et on treatment with carbon monoxide and di-t-butyl peroxide in the presence of palladium(II) chloride and copper(II) chloride357. Carbamic esters 304 and 305 are also obtained from aliphatic amines and ortho carbonates (R30)4C358. Vinyl carbamates R12NC02CH=CHR2 are produced from secondary aliphatic amines, acetylenes R2C=CH (R2 = Bu or Ph) and carbon dioxide in the presence of ruthenium(III) chloride359. 

Action of Aliphatic Amines on Slow Oxidation of Acetaldehyde and Ethyl Ether, and on Decomposition of Organic Peroxides in the Gas Phase... 

Aliphatic amines have much less effect on the later reactions of the gas-phase oxidation of acetaldehyde and ethyl ether than if added at the start of reaction. There is no evidence that they catalyze decomposition of peroxides, but they appear to retard decomposition of peracetic acid. Amines have no marked effect on the rate of decomposition of tert-butyl peroxide and ethyl tert-butyl peroxide. The nature of products formed from the peroxides is not altered by the amine, but product distribution is changed. Rate constants at 153°C. for the reaction between methyl radicals and amines are calculated for a number of primary, secondary, and tertiary amines and are compared with the effectiveness of the amine as an inhibitor of gas-phase oxidation reactions. 

Action of Aliphatic Amines on Decomposition of tert-Butyl Peroxide. The rate of decomposition of tert-butyl peroxide is not greatly affected... 

Even large amounts of aliphatic amines do not alter the rate of decomposition of tert-butyl peroxide, but they do slow down the rate of decomposition of ethyl tert-butyl peroxide. 

The results given in this paper show that aliphatic amines do not catalyze the decomposition of peroxides, and compared with their effect at the start of reaction, they have much less effect on the later stages of oxidation, although they appear to retard the decomposition of peracetic acid. The reactions of radicals with aliphatic amines indicate that an important mode of inhibition is most probably by stabilization of free radicals by amine molecules early in the chain mechanism, possibly radicals formed from the initiation reaction between the fuel and oxygen. For inhibition to be effective, the amine radical must not take any further part in the chain reaction set up in the fuel-oxygen system. The fate of the inhibitor molecules is being elucidated at present. 

H. S. Olcott (University of California, Berkeley, Calif.) We have studied the effects of aliphatic amines on the autoxidation of a fish oil and squalene in air at moderate temperatures. There was little protection unless phenolic-type inhibitors were also added, in which case secondary amines were more effective than primary or secondary amines. However, at 70 °C. trioctylamine alone protected the fish oil, whereas at lower temperatures it did not (2). Further study revealed that peroxides react with trioctylamine to yield some dioctylhydroxylamine which has antioxidant properties (1). These and other observations (3) indicate that... 

Among the oxidative procedures for preparing azo compounds are oxidation of aromatic amines with activated manganese dioxide oxidation of fluorinated aromatic amines with sodium hypochlorite oxidation of aromatic amines with peracids in the presence of cupric ions oxidation of hindered aliphatic amines with iodine pentafluoride oxidation of both aromatic and aliphatic hydrazine derivatives with a variety of reagents such as hydrogen peroxide, halogens or hypochlorites, mercuric oxide, A-bromosuccinimide, nitric acid, and oxides of nitrogen. 

Hydroperoxides and peroxides oxidize primary and secondary aliphatic amines to imines. Thus f-butyl hydroperoxide oxidizes 4-methyl-2-pentyl-amine to 2-(4-methylpentylidene)-4-methyl-2-pentylamine in 66% yield [29]. Di-r-butyl peroxide reacts in a similar manner [29]. However, this reaction is... 

AMINES - LOWER ALIPHATIC AMINES] (Vol 2) tert-Butyl tert-cumyl peroxide [3457-61-2]... 

Nitriles are also the usual products of oxidation of aliphatic amines RCH2NH2 by nickel peroxide and lead(IV) acetate. Aliphatic azo compounds can be prepared from these primary amines by first converting them into ulfamides (6), these then being oxidized with sodium hypochlorite or (better) r butyl hypochlorite (Scheme 9). A few aliphatic azo compounds can be formed in good yield by direct oxidation of r-alkylamines for example, AIBN was formed (86%) by oxidation of the amine Me2C(CN)NH2 with sodium hypochlorite. A special case of azoalkane foimation is the synthesis of chlorodiazirines (7) from amidines RC(= NH)NH2 by oxidation with sodium hypochlorite. ... 

The purpose of preparing aliphatic amine oxides is usually their thermal decomposition to cis alkenes and N,N-dialkylhydroxylamines (Cope rearrangement) [156, 161, 1187]. Thus A, A -dimethylcyclohexylmethylamine is oxidized with 30% hydrogen peroxide in methanol to its oxide, whose decomposition at 90-100 °C at 10 mm of Hg and at 160 °C for 2 h furnishes 79-88% of methylenecyclohexane and 78-90% of A, A -dimethylhydroxyl-amine [161], Another example is the preparation of cw-cyclooctene from dimethylcyclooctylamine (equation 502) [1187]. 

Ammonia was oxidized with hydrogen peroxide in the presence of TS-1 first to hydroxylamine and then, further to nitrogen oxides if the hydroxylamine was not trapped. When this reaction was run in the presence of a ketone, the oxime was selectively formed (Eqn. 21.8).33 Oximes were also produced by the oxidation of primary aliphatic amines with TS-1 or TS-2 and hydrogen peroxide at ambient temperature. Linear amines such as n-propyl amine (6) gave the oxime in 73% yield at 32% conversion over the TS-1 catalyst (Eqn. 21.9).3 The isopropyl amine (7) was oxidized with somewhat higher selectivity over the larger pore TS-2 catalyst (Eqn. 21.10).34 Primary aryl amines were oxidized to the symmetrical azoxybenzenes under these conditions (Eqn. 21.11). ... 

Drugs that are susceptible to oxidation of carbon-hydrogen bonds include ethers (which oxidise to form highly explosive peroxides), aliphatic amines (which oxidise at the a hydrogen atom) and aldehydes (which are easily oxidised to carboxylic acids and peroxy acids). Examples of these reactions are shown in Figure 8.6. 

Homer and Hoffmann" reported use of triphenylphosphine for the deoxygcnution of azoxy compounds to uzo compounds, of peroxides to ethers, of nitrones to Schiff bases, and of aliphatic amine oxides to amines. The lalier reiicliun was done in nfliKina iieatic anld and under these contillloni the N-oxides of pyridine and quinoline... 

ACETOPHENONE (98-86-2) C,H,0 Combustible liquid. Forms explosive mixture with air [explosion limits in air (vol %) 1.1 to 6.7 flash point 180°F/82°C oc autoignition temp 1058°F/570°C Fire Rating 2]. Violent reaction with strong oxidizers. Inconq)atible with strong acids, aldehydes, aliphatic amines, cyanides, isocyanates, oxidizers, perchloric acid, hydrogen peroxide and other peroxides. Reacts with many acids and bases, reducing... 

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