F-Alkylamines

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 oxicUzed 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 f-alkylamines for example, AIBN was formed (86%) by oxidation of the amine Me2C(CN)NH2 with sodium hypochlorite. A special case of azoalkane formation is the synthesis of chlorodiazirines (7) from amidines RC(=NH)NH2 by oxidation with sodium hypochlorite. ... 

Dehydrohalogenation. f-Alkylamines react with epichlorohydrin in methanol at 20-25° to give l-r-alkylamino-3-chloro-2-propanols. On dehydrohalogenation... 

Amine functionalities also may be created on polysaccharides (Section 4.3, this chapter). The reducing ends of carbohydrate molecules (or generated aldehydes) may be reacted with small diamine compounds to yield short alkylamine spacers that can be used for subsequent conjugation reactions. Hydrazide groups may be similarly created using f z s-hydrazide compounds (Sections 4.5 and 4.6, this chapter). 

It has been reported that the UV spectra of l,2,3-benzotriazin-4(3/f)-one (10, R = H), the corresponding triazinethione (39, R = H) and the 4-alkylamino-l,2,3-benzotriazines (56) formed by treatment of 39, R = H, with alkylamines are nearly identical, and this has been taken as evidence that the compounds 56 actually exist as the 3,4-dihydro-4-imino tautomers. This claim has not, however, been substantiated, and, in the absence of more definitive evidence, structure 56 is almost certainly the more accurate representation for these compounds. 

A less frequently used method involves the condensation of trimethylsilyl alkylamines with f-butyl hydroperoxide. A 20% yield of trunethyl(f-butylperoxy)silane has been obtained (equation 26). ... 

N-Tosylated p-hydroxy alkylamines (which can be easily hydrolyzed to f -hydroxyamines79h) can be prepared797 by treatment of alkenes with the trihydrate of Chloramine-T637 and a catalytic amount of 0s04. In some cases yields can be improved by the use of phase-transfer catalysis.798 The reaction has been carried out enantioselectively.799 In another procedure, certain p-hydroxy secondary alkylamines can be prepared by treatment of alkenes with the osmium compounds /-Bu—N=0s03, followed by reductive cleavage with LiAlH4 of the... 

The assembly of functionalized nanostructured silica with uniform pore channels using neutral alkylamine surfactants (S°I° -> HMS) and non-ionic alkylpolyethyleneoxide surfactants (N°I° —> MSU-X) provides many advantages over conventional electrostatic assembly pathways (S+f, etc.). In contrast with electrostatically assembled MCM-41-type materials, mesostructured adsorbents produced by non-electrostatic assembly methods typically possess pore channel structures and particle morphologies which improve their ability to interact with targeted adsorbate species. Moreover, non-electrostatic assembly pathways are well-suited for the direct synthesis of functionalized mesostructured silica by one-step preparation processes under ambient temperature, neutral pH conditions. The environmental application of such materials for the treatment of mercury-contaminated water is also demonstrated. 

Reaction of perfluoropropene with diethylamine yields (F)-fluoroenaminc 3 and fluoro-alkylamine 4 in a 1 1 or 3 1 mixture (depending on the reaction conditions used). This mixture is known as Ishikawa s reagent and can be used (without separation) for the transformation of alkyl alcohols to fluoroalkanes (see Vol. ElOb/Part 1. p99).218... 

Chatgilialoglu C, Castelhano AL, Griller D (1985) Structures and optical absorption spectra of some sulfuranyl radicals in solution. J Org Chem 50 2516-2518 D Alessandro N, Bianchi G, Fang X, Jin F, Schuchmann H-P, von Sonntag C (2000) Reaction of superoxide with phenoxyl-type radicals. J Chem Soc Perkin Trans 2 1862-1867 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 Das S, Schuchmann MN, Schuchmann H-P, von Sonntag C (1987) The production of the superoxide radical anion by the OH radical-induced oxidation of trimethylamine in oxygenated aqueous solution. The kinetics of the hydrolysis of (hydroxymethyl)dimethylamine. Chem Ber 120 319-323... 

Thus, one can conclude that the 3-benzylamino group in 311 g as well as ben-zylamine itself is oxidized into their corresponding imines easier than ordinary alkylamines. When both reactants do not contain a benzylamino fragment, the cyclohexylamino group is oxidized first. If both benzylamino and cyclohexylamino functions are absent in the reactants, the process starts from oxidation of a 3-alkylamino group as in 311e,f,k. Heterocyclizations described here represent a novel approach to condensed imidazoles and imidazolines. 

The reductive-trimethylsilylation, via either a chemical (Li/HMPA/THF) or an electrochemical (undivided cell/sacrificial anode) process, led to the synthesis of 1-(trimethylsilyl)alkylamines (RSMAs).191 Thus, l-(trimethylsilyl)f-amylamine was prepared in 67% yield from pivalaldehyde iV-(trimethylsilyl)imine, after hydrolysis of the intermediate silazane. 

Oxidative dealkylation of tert-amines.1 Oxidation of tert-N-methylamines with f-BuOOH (2 equiv.) catalyzed by this ruthenium complex results in a-(t-butyl-dioxy)alkylamines. N-Methyl groups are oxidized selectively in the presence of... 

Bukowski, J. F., Morita, C. T., and Brenner, M. B. (1999). Human gamma delta T cells recognize alkylamines derived from microbes, edible plants, and tea Implications for innate immunity. Immunity 11(1), 57-65. 

Ammonia and other amines are good nucleophiles in s2 reactions. As s result, the simplest method of alkytamine synthesis is by alkylation f ammonia nr an alkylamine with an alkyl halide. If ammonia is used, s pri-... 

Methods for the chlorination of secondary amines, secondary amides and imides have been reviewed. Secondary alkylamines can be chlorinated by f-butyl hypochlorite at low temperature, or by sodium hypochlorite or IV-chlorosuccinimide. A/-Bromination and IV-iodination can be brought about by using the appropriate halogen, but these A/-halodialkylamines are unstable and are rarely isolated. A -Flu-oroamines and -fluoroamides are also rare. The A/-fluoroimide (CP3S02)2NF, has, however, been prepared by direct fluorination with fluorine. It is a stable liquid which shows promise as a fluorinating agent for aromatic compounds. ... 

The high reactivity of N-H bonds has also been exploited to produce N-F denvatives without significant substitution on neighbonng C-H bonds, Diethyl-phosphoramidates of ammonia, alkylamines, and a,o> diaminoalkanes were fluor-inated in polar solvents to produce difluoroamine [51], A(,A(-difluoroalkylamines, and a,a)-bis(/VJV-difluoroainino)alkanes [52] Acetamide undergoes fluonnation to give modest yields of N,N difluoroacetatnide and acetyl fluonde when fluorinated... 

The distinction between enantiomeric species is normally made by the use of a chiral shift reagent (Section F.4). However, it has been reported that in certain circumstances sueh a distinction can be achieved with an achiral shift reagent. (497) Enantiomeric shift differences AA<5 are induced by Ln(fod)3 for partly resolved alkylamines (Fig. 10). The values... 

Selective oxidative demethylation of tertiary methyl amines is one of the specific and important functions of cytochrome P-450. Novel cytochrome P-450-type oxidation behavior with tertiary amines has been found in the catalytic systems of low-valent ruthenium complexes with peroxides. These systems exhibit specific reactivity toward oxidations of nitrogen compounds such as amines and amides, differing from that with RUO4. It was discovered in 1988 that low-valent ruthenium complex-catalyzed oxidation of tertiary methylamines 53 with f-BuOOH gives the corresponding a-(f-butyldioxy)alkylamines 54 efficiently (Eq. 3.70) [130]. The hemiaminal type 54 product has a similar structure to a-hydroxymethylamine intermediate derived from the oxidation with cytochrome P-450. 

The best method for the preparation of A-alkylamide peptides employs 5-(4- [[(9//-fluoren-9-ylmethoxy)carbonyl](alkyl)amino]methyl -3,5-dimethoxyphenoxy)valeric acid [(R)-PAL handle, 29],f l which is derived from the PAL handle. The (R)PAL handle, when used in the same way as PAL, would transfer the alkylamine to the peptide. Similarly, the use of N-alkyl XALP 1 or A-alkyl Rink resinst °°l also gives rise to A-alkylamide peptides. The same conditions as those used to release peptides from PAL, Rink, and XAL apply for the A-alkyl analogues. The preparation of A/,A-dialkylamide peptides requires a backbone attachment strategy (see Section 4.3.1.2.5).f l... 

The P/F mol ratio is usually 1/1 to 1/3, but preferably 1/1.5 to 1/2.0. The basic catalysts to be used then should be hydroxides of barium, sodium, potassium and ammonium carbonates of sodium and potassium alkylamines, etc. The quantity of these catalysts to be used is 0.005 to 0.1 mol against 1 mol of P. The preferable quantity of these catalysts is 0.01 to 0.05 mol. After these materials, in aqueous solution, react at a temperature below lOO C they are neutralized with an appropriate acid and then dehydrated to provide a liquid-type resol. Representative properties of resol are shown in Table 57. 

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