Alkylene Diamines

H. Wirtz, H. Hoffmann, W. Ritschel, M. Hofinger, M. Mitzlafif, and D. Wolter. Optionally quatemized fatty esters of alkoxylated alkyl-alkylene diamines (Gegebenenfalls quatemierte Fettsaureester von oxyalkylierten Alkyl-Alkylendiaminen). Patent EP 320769, 1989. 

Poly(amidoamine)-(PAMAM-Starburst)-Monodendrons Among the first Starburst (Cascade) syntheses we performed in the early 1980s [83] involved partially masked (differentiated) initiator cores. For example dodecyl-amine, hydroxyalkyl amines or partially protected alkylene diamines were used as initiator cores and submitted to sequential (a) Michael addition with methyl acrylate followed by (b) reaction with an excess of ethylene diamine to give in situ branch cell construction in a divergent manner. The resulting products were core functionalized monodendrons as shown below ... 

Many examples have been reported of the replacement of a halogen by an amine to produce type B3 co-oligomers, e.g., the tetrasubstituted ethylenes (118 X = CH2, O)144 obtained in high yields by heating chloro-trifluoroethylene with piperidine and morpholine (respectively) at 80°. The reaction of 1,3-dimethyl-4-chlorouracil with 0.5 mole of an alkylene-diamine (in the presence of excess triethylamine) yielded the bisuracilyl-... 

Studies of the reactivity of l,3-a 5a-oxy(tetraethyleneoxy) derivative (99) have been extended to reactions with alkylene diamines. Substitution takes place at the PCI centre as a consequence of the interaction between the incoming nucleophile and the crown ether ligand already present, yielding compounds (100), (101) and (102). Only for H2N(CH2)3NH2 was the formation of a spiro derivative (103) was observed. Treatment of (99) with an excess of nucleophilic reagents leads to substitution of all chlorine... 

The reaction of carbon disulfide with 1,2-alkylene diamines (I) yields N-(2-aminoethyl) dithiocarbamic acids (II) which split off hydrogen sulfide thermally to give imidazolidine-2-thiones (III) (Hofmann-process). The simplest example, the reaction of carbon disulfide with ethylenediamine, is described in Organic Synthesis (5). The reaction is general for N,N -dialkyl-, N,N -diaryI, as well as for N,N -bis-(arylakyl) ethylene diamines. The rate of reaction is determined by the basicity of the diamine. Electron-donor substituents in the para-position of N-aromatically substituted ethylene diamines accelerate dithiocarbamate formation electron-acceptor groups retard it. 

Instead of 1,2-alkylene diamines, 2-unsubstituted imidazolidines (the reaction product of diamines with formaldehyde) (V) may also be used. The intermediates then are yellow addition compounds, the perhydro-l,3,6-thiadiazepine-2-thiones (VI) (321), which decompose on heating to the imidazolidine-2-thiones (III) and thioformaldehyde (110). This reaction though is not general. 

Polyamides are obtained either by the condensation of a dicarboxylic acid and an alkylene diamine or by the head-to-tail condensation between an amino carboxylic acid or the corresponding lactam. Polyamides may have aliphatic or aromatic chain backbones. Aliphatic polyamides (nylon) have the most important commercial applications, mainly in the manufacture of fibres. Nylon-6 and nylon-6,6 account for around 85% of all nylon currently used. Nylon-6 is derived from the polymerization of e-caprolactam, whereas nylon-6,6 is obtained by the condensation of hexamethylene diamine and adipic acid. 

Table 14.48 Vapor Pressures of Alkylene Diamines and Other Amines (19)...

In 1978 we reported the synthesis of poly(amide enamlnes) by the reaction of a diamine with diketene in aprotic solvents. The reaction proceeds via the formation of acetacetoamides which condense further with the amines giving the poly(amide enamines), 2 Pol)nners derived from alkylene diamines with four to twelve carbons were found to be biodegradable, supporting the... 

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