Hydroxyl group aliphatic amines

Inspired by the results of aromatic-ring hydroxylation from the laboratory of Karlin and co-workers, a few groups provided further examples of such reactivity, including some structurally characterized complexes of modified m-xylyl-based pyridine-donor ligands (Schiff base and non-Schiff base acyclic ligands), as well as aliphatic amine donor ligands (179) (Cu-Cu 2.990 A),169 (180) (Cu-Cu 3.015 A),170 and (181) (Cu-Cu 2.999 A).171 172 A m-xylyl-based ligand system that was used by Mukherjee and co-workers in the formation of complex (181) also resulted in the isolation of a bis(/i-hydroxo)dicopper(II) complex (182) (Cu-Cu 3.004 A).171,172 Casella and co-workers demonstrated that when their dicopper(I) complex... 

Acetyltransferases catalyze the acetylation of amino, hydroxyl, and thiol functional groups. Acetylation of hydroxy and thiol groups is comparatively rare and of much less importance in alkaloid metabolism than reactions with amino functional groups. The types of amines that are acetylated include arylamines (the major route of metabolism in many species), aliphatic amines, hydrazines, sulfonamides, and the a-amino group of cysteine conjugates. The purification, physical properties, and specificity of the N-acetyltransfereases have been reviewed (116-118). 

Oxidation Carbon-Nitrogen Systems. Primary amines may be hydroxylated at the nitrogen atom (N-oxidation) to yield the corresponding hydroxylamine. Alternatively, primary alkyl or arylalkyl amines may undergo hydroxylation at the a-carbon to give a carbinolamine that decomposes to an aldehyde and ammonia (through the process of oxidative deamination). Secondary aliphatic amines may lose an alkyl group first N-dealkylation) prior to oxidative deamination. 

Telomers 422 (n = 2) and other 4-halogeno-l,3-dioxolan-2-ones were shown288 to react readily with ammonia or primary aliphatic amines, with formation of 4-hydroxy-2-oxazolidones (460). The latter, for which the trans arrangement of the hydrogen atoms of the oxazoli-done ring was deduced from H-n.m.r. data, readily underwent replacement of the hydroxyl group by a phenyl group on reaction with... 

The formation of sulfate esters is a major route of conjugation for various types of hydroxyl group, and may also occur with amino groups. Thus, substrates include aliphatic alcohols, phenols, aromatic amines, and also endogenous compounds such as steroids and carbohydrates (Figs. 4.56 and 4.57). 

At high pH (10), Traut s reagent also is reactive with aliphatic and aromatic hydroxyl groups, although the rate of reaction with these groups is only about 0.01 that of primary amines. In the absence of amines, however, carbohydrates such as agarose or cellulose membranes can be modified to contain sulfhydryl residues (Alagon and... 

Morphine contains one tertiary aliphatic amine, one phenolic hydroxyl group, one secondary alcohol, and one ether. 

Cockram and Wheeler, 1927, 1931 Blayden et al 1948 Wender et al., 1981). These studies, as well as later work (Dryden, 1950, 1951 Given, 1984), showed that significant yields of extracts, often as high as 35 to 40%, can be obtained by using pyridine, certain heterocyclic bases, or primary aliphatic amines (which may, but need not, contain aromatic or hydroxyl substituents). Secondary and tertiary aliphatic amines are often much less effective insofar as more than one alkyl group on the amine appears to present steric problems that interfere with the interaction between the solvent and the coal. 

In the well-recognized epoxy-aliphatic amine reaction, the primary or secondary amine adds to the epoxy ring, forming a tertiary amine, as shown in Fig. 5.2 (top). The formed hydroxyl groups accelerate the amine curing, and with excess epoxy present, the secondary hydroxyl groups can also add to the epoxy ring, as shown in Fig. 5.2 (bottom). 

Unsymmetrical secondary amines are readily prepared in good yields by the catalytic reduction of Schiff bases at moderate temperatures in high-or low-pressure equipment. Many examples have been cited. The intermediate imines are prepared from primary amines and aldehydes—very seldom from ketones—and may be used without isolation (cf. method 431). For the preparation of aliphatic amines, e.g., ethyl-w-propylamine and n-butylisoamylamine, a prereduced platinum oxide catalyst is preferred with alcohol as the solvent. Schiff bases from the condensation of aromatic aldehydes with either aromatic or aliphatic amines are more readily prepared and are reduced over a nickel catalyst. In this manner, a large number of N-alkylbenzylamines having halo, hydroxyl, or methoxyl groups on the nucleus have been made. Reductions by means of sodium and alcohol and lithium aluminum hydride have also been described,... 

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