Aliphatic alkylamines

Aliphatic Alkylamines. The aliphatic alkylamines are made in a variety of ways. For the lower amines, the action of an alcohol on ammonia or an amine in the vapor phase over aluminum oxide is a common method of preparation (see Chap. 8). For the higher amines, the action of an alkyl halide on ammonia in the liquid phase, often in the presence of the corresponding alcohol, is frequently used. Heat is often needed in the liquid-phase reactions, and autoclaves are then needed. The dialkyl sulfates are of particular importance because of their higher boiling points and ability to act as an alkylating agent on being heated in ordinary nonpressure vessels. 

The reactions of chloramine are not generally successful with N-chloroalkylamines. Therefore it was surprising that the diaziridine synthesis occurred smoothly from aliphatic Schiff s bases and V-chloro-alkylamines [Eq. (33), Table VII]. As can be seen from examples... 

The flow-cell design was introduced by Stieg and Nieman [166] in 1978 for analytical uses of CL. Burguera and Townshend [167] used the CL emission produced by the oxidation of alkylamines by benzoyl peroxide to determine aliphatic secondary and tertiary amines in chloroform or acetone. They tested various coiled flow cells for monitoring the CL emission produced by the cobalt-catalyzed oxidation of luminol by hydrogen peroxide and the fluorescein-sensitized oxidation of sulfide by sodium hypochlorite [168], Rule and Seitz [169] reported one of the first applications of flow injection analysis (FTA) in the CL detection of peroxide with luminol in the presence of a copper ion catalyst. They... 

Advantages include in this CL system the reagent is regenerated and it can be recycled, and derivatization is not required for many classes of compounds. Many aliphatic amines such as alkylamines, amino acids, proteins, antibiotics such as erythromycin and clindamycin, and NADH, among others can par-... 

Another situation is observed when salts or transition metal complexes are added to an alcohol (primary or secondary) or alkylamine subjected to oxidation in this case, a prolonged retardation of the initiated oxidation occurs, owing to repeated chain termination. This was discovered for the first time in the study of cyclohexanol oxidation in the presence of copper salt [49]. Copper and manganese ions also exert an inhibiting effect on the initiated oxidation of 1,2-cyclohexadiene [12], aliphatic amines [19], and 1,2-disubstituted ethenes [13]. This is accounted for, first, by the dual redox nature of the peroxyl radicals H02, >C(0H)02 and >C(NHR)02 , and, second, for the ability of ions and complexes of transition metals to accept and release an electron when they are in an higher- and lower-valence state. 

Other examples are acetoacetates alkylamines and alkylhalides/acid halides ethers esters chloroformates ketones lactames lactones malonates mercaptanes and orthoesters in aliphatics catechol/hydroquinone/resorcinol, cresidines haloaromatics in aromatics and coumarines, cyanuric chloride, picolines, quinolines, and thiazoles in heterocylics. 

B.p. Enoksson (of Sweden), BritP 1147967(1969) CA 71, 23402n (1969) (AN with water-resistant and anticaking props was obtd by coating its particles with 0.05—0.1% of a mixt contg 2—10 moles of an alkylamine and 1 mole of an aliphatic acid. The acid and amine contained 12—20 carbon atoms. Stearylamine and stearic acid were used in one example)... 

Similar to other tertiary aliphatic amines, quinuclidine easily forms salts with mineral and organic acids, and quaternary derivatives with alkyl halides. However, the rates of reaction of alkyl iodides with quinuclidine are significantly higher than with tertiary aliphatic amines.32 For example, quinuclidine reacts with methyl iodide 50 times faster, and with isopropyl iodide 700 times faster, than does triethylamine. The addition compound of trimethylborane with quinuclidine is more stable than the corresponding adducts of tri-alkylamines. These results can be explained by the almost total... 

The existence of the alkylamines was predicted by J. von Liebig,1 1837 in 1849, A. Wurtz obtained the primary alkylamines and in 1851, A. W. Hofmann prepared the primary, secondary, and tertiary alkylamines, and also the alkylammonium bases or the quarternary ammonium bases in which all four atoms of the ammonium group are replaced by the alkyl radicles. The basic character of ammonia is retained by the amines, and since the alkyl radicles are themselves basic, the aliphatic amines are even more basic than ammonia itself. W. Ostwald made an estimate of the basicity of the ethyl ammonias, and found the relative strengths of these bases ... 

Das S, von Sonntag C (1986) Oxidation of trimethylamine by OH radicals in aqueous solution, as studied by pulse radiolysis, ESR and product analysis. The reactions of the alkylamine radical cation, the aminoalkyl radical and the protonated aminoalkyl radical. Z Naturforsch 41b 505-513 Dixon WT, Norman ROC, Buley AL (1964) Electron spin resonance studies of oxidation. Part II. Aliphatic acids and substituted acids. J Chem Soc 3625-3634 Draper HH, Squires EJ, Mahmoodi H, Wu J, Agarwal S, Hadley M (1993) A comparative evaluation of thiobarbituric acid methods for the determination of malondialdehyde in biological materials. Free Rad Biol Med 15 353-363... 

The most conspicuous property of aliphatic amines, apart from their fishy smell, is their high basicity, which usually precludes N-alkylations under acidic reaction conditions (last reaction, Scheme 6.3). Hence, alkylation of amines with tertiary alkyl groups is not usually possible without the use of highly stabilized carbocations which can be formed under basic reaction conditions. Rare exceptions are N-alkyla-tions of amines via radicals (Scheme 4.2), copper-catalyzed propargylations (Scheme 6.3), and the addition of amines to some Michael acceptors and allyl palladium or iridium complexes. Better strategies for the preparation of tert-alkylamines include the addition of Grignard reagents to ketone-derived imines [13] or the reduction of tert-alkyl nitro compounds. 

Food, flavors consist of numerous compounds, none of which alone is characteristic of specific food. Classes of compounds which emcompass food flavors are - hydrocarbons (aliphatic, ali-cyclic, aromatic) carbonyls (aldehydes, ketones) carboxylic acids, esters, imides, anhydrides alcohols, phenols, ethers alkylamines, alkylimines aliphatic sulfur compounds (thiols, mono-, di- and tri-sulfides) nitrogen heterocyclics (pyrroles, pyrazines, pyridines) sulfur heterocylics (thiophenes, thiazoles, trithiolane, thialidine) and oxygen-heterocyclics (lactone, pyrone, furan). Discussion will be limited to striking developments in heterocyclics. 

The alkylamine hydrate inclusion compounds form a large variety of structures. Phase diagram studies at the end of the last century [7651 (see Tkble 21.3), and an extensive series of phase diagram studies carried out between 1970 and 1981 [798], showed that aliphatic amines form a large variety of hydrates. Relatively few of these have been studied by X-ray crystal structure analysis and none by neutron diffraction [433, 799]. These hydrates differ from the gas hydrates and the alkyl ammonium salt hydrates in that there appear to be no definite structural types into which several hydrates can be classified. Hitherto, a different crystal structure has been observed for every alkylamine hydrate studied. In this respect, they resemble low hydrated crystals. 

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. ... 

Good yields of fluorohydrins 4/5 can be achieved even from simple aliphatic epoxides using 70 % hydrogen fluoridc/pyridine by careful control of the reaction conditions,but the regioselectivity may be considerably lower than with alkylamine hydrofliiorides. 

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