Aminoalkyl derivatives

Acid-catalyzed aminomethylations of 5W-dibenz[/>,/]azepine (5) in ethanolic solution with formaldehyde and a secondary amine yield the 2-(aminoalkyl) derivatives, e.g. 6.186 If acetic acid is used as the solvent, however, then 2,8-bis(aminoaIkylatiou), e.g. formation of 7, results. 

In some instances, reducing sugars are present that can be reductively aminated without prior periodate treatment. A reducing end of a monosaccharide, a disaccharide, or a polysaccharide chain may be coupled to a diamine by reductive amination to yield an aminoalkyl derivative bound by a secondary amine linkage (Figure 1.96). Also see Section 4.6, this chapter, for an extensive discussion on carbohydrate modification techniques. 

This versatile water-soluble reactant has been evaluated in wool and nylon dyeing. The nucleophilic aminoalkyl derivatives of orthodox aminochlorotriazine dyes behave like traditional acid dyes on wool owing to their zwitterionic character under neutral-dyeing conditions (Scheme 7.65). Improved wet fastness can be achieved using the reactant XLC... 

More controlled and efficient fixation is possible when the reactant is applied as a pretreating agent [146]. If nylon given such a pretreatment is subsequently dyed with the conventional chlorotriazine dye Cl Reactive Red 3 (7.2), the substantivity and fixation of the latter are markedly lowered because the anionic XLC residues have reacted with N-terminal amino groups in the fibre. Treatment of the modified nylon with ammonia, however, restores some degree of dyeability. Opposite effects are observed if Cl Reactive Red 3 is reacted with ethylenediamine to form an aminoalkyl derivative (7.131). This nucleophilic dye exhibits a high degree of fixation only on the modified nylon that has been pretreated with XLC. 

The alkylation with alcohols and amines can lead to alkyl derivatives or a-hydroxy and a-aminoalkyl derivatives according to the nature of the heteroaromatic base and the reaction conditions. The intermediate products in both cases are, however, the a-hydroxy and a-aminoalkyl dihydro derivatives, which can be aromatized by disproportionation or oxidation, while the loss of water or ammonia leads to the alkyl derivatives (Scheme 7). 

Mule, A. Pirisino, G. Manca, P. Satta, M. Peana, A. Savelli, F. Tertiary-Aminoalkyl Derivatives of Quinoxalinones and of Aza- and Diazaquinoxali-nones With Analgesic Activity, Farmaco, Ed. Sci. 1988, 43, 613. 

Secondary and tertiary aminoalkylbenzotriazoles (108) react with pyrrole, indole, and their N-methyl analogues under mild conditions in the presence of a Lewis acid to afford selectively the corresponding secondary or tertiary aminoalkyl derivatives (Scheme 22) (92T4971). A,A-Bis(alk-oxymethyl)amines can also be used to give secondary alkylamines, which operate via reactive iminium salts formed by treatment with trimethylsilyl chloride (90TL4229). 

Formation of Carbon-Carbon Bonds In the presence of aluminum chloride, benzene adds to aairidine" to give 0-aminoalkyl derivatives (Eq. 71). 

As mentioned above, (7-aza-3-indolyl)acetonitrile (129) was reduced catalytically to give 7-azatr3rptamine (131). Other 7-azatryptamines prepared similarly are 1-methyl, 1-benzyl, 2-methyl, and l-(2-aminoethyl). This patent also describes several other 1-, 2-, and 3-(aminoalkyl) derivatives of the four azaindole isomers. The several 4-, 5-, 6-, and 7-azaindolylalkanonitriles were also treated with hydrolylamine to give amidoximes and with hydrogen chloride in chloroform, followed by ammonia to give amidines. ... 

Artemisinin has been converted in two steps into the stable trioxane isobutene dimer 41. Reactions at the linking unit leave the trioxane fragments intact and allow the synthesis of a variety of dimers that possess desirable pharmacological properties <03JMC1060>. 10-Bromoalkyl and 10-aminoalkyl derivatives of deoxoartemisinin have been prepared and used to form dimers and a trimer in which artemisinin residues are linked through alkylamide and alkylthio functions <03JMC987>. 

Mannich reaction The condensation of CH activated compound with a primary or secondary amine and a non-enolizable carbonyl compound to afford aminoalkylated derivatives. 274... 

SAR of Primaquine. Structural modifications of pamaquine produced the unsubstitutedprimary aminoalkyl derivative i.e., primaquine, whose relatively more predominant therepeutic activity and significantly much lower toxicity (specifically the tendency for causing hemolysis) essentially replaced pamaquine virtually as the most well recognized tissue schizonticide of choice. 

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