Aliphatic chains polyamines

Complexation of Cd with a series of polyamine macrocycles, but also related open-chain polyamines, comprising or attached to the 2,2 -bipyridine (bipy) and 1,10-phenanthroline (phen) moieties, has been studied by combined UV/vis spectrometry and potentiometry.24 Formation constants and distribution diagrams of the species present have been evaluated. As a result the thermodynamic stabilities, i.e., the formation constants, are lower for the bipy- and phen-contain-ing ligands than those for Cd complexes with aliphatic oligoaza macrocycles containing the same number of N donors. The probable reason is loss of flexibility of the ligands caused by the size and stiffness of the inserted heteroaromatic moieties. 

Properties Short-chain aliphatic poly amine Oxyalkylated short-chain poly amine Long-chain polyamine adduct Aromatic poly amine adduct Polyamide... 

The synthesis of secondary amines from azides is efficient in terms of chemos-electivity [57] and has found valuable applications in the preparation of diamines [58,59], m-alkylaminoboronic esters [60], and in Diels-Alder-based amination reactions [61]. A convenient general route to open-chain polyamines, which play major roles in cellular differentiation and proliferation, has also been developed using the reductive alkylation of aliphatic aminoazides by (co-halogenoalk-yi)dichloroboranes as a key step [62] (Scheme 21). 

Interesting protonation patterns are shown by the ditopic hexaazacycloalkanes, 28-32, containing two polyamine units separated by long aliphatic chains (Table 2). Such molecules represent for protons what ditopic ligands are for metal ions. As shown in Table 2, the two triaminic subunits behave as almost independent entities toward protonation, since protons can alternatively occupy the two subunits, which are far apart from each other, giving rise to similar values of the equilibrium constants for the same protonation step in each subunit. ... 

Table 6 contains tabulated results derived from Table 5. In general it appears that if a polyamine inhibits one or two bacteria, they will inhibit a majority of others, i.e., the polyamines appear to be largely noninhibitory or widely inhibitory. Second, there is a distinct trend with respect to length of the aliphatic chain such that the polyamines derived from 1,6->hexanediamine and 1,7-diaminoheptane exhibit wide inhibition whereas those derived from 1,10-diaminodecane and 1,12-diaminododecane are noninhibitory.

Polyamine conjugates with long aliphatic chains... 

In cases where either the polyamine moiety differs distinctly from the commercially available building blocks or polyamines with more diversity are required, the backbone is preferentially generated by stepwise and modular elongation. Diversity can be achieved by the introduction of different aliphatic chains between the nitrogens, branching of the skeleton in aUcyl-or amino position, and the introduction of other functional groups into the backbone. This finally opens access to numerous compounds that are different in detail but structurally closely related. 

This reaction is reported to proceed at a rapid rate, with over 25% conversion in less than 0.001 s [3]. It can also proceed at very low temperatures, as in the middle of winter. Most primary substituted urea linkages, referred to as urea bonds, are more thermally stable than urethane bonds, by 20-30°C, but not in all cases. Polyamines based on aromatic amines are normally somewhat slower, especially if there are additional electron withdrawing moieties on the aromatic ring, such as chlorine or ester linkages [4]. Use of aliphatic isocyanates, such as methylene bis-4,4 -(cyclohexylisocyanate) (HnMDI), in place of MDI, has been shown to slow the gelation rate to about 60 s, with an amine chain extender present. Sterically hindered secondary amine-terminated polyols, in conjunction with certain aliphatic isocyanates, are reported to have slower gelation times, in some cases as long as 24 h [4]. 

Amines. Aliphatic mono-, di-, and polyamines derived from fatty and main acids make up this class of surfactants. Primary, secondary, and tertiary monoamines with Qg alkyl or alkenyl chains constitute the bulk of diis class. The products are sold as acetates, naphdienales, or oleates. Principal uses are as ore-flotation agents, corrosion inhibitors, dispersing agents, wetting agents for asphalt, and as intermediates for the production of more highly substituted derivatives... 

Primary and secondary di- and polyamines are used as chain extenders and cross-linkers. Aromatic amines are more reactive than aliphatic ones. 

Flexiblization. Aliphatic diepoxide reactive diluents enhance the flexibility or elongation by providing chain segments with greater free rotation between cross-links. Polyaminoamide hardeners, based on aliphatic polyamines and dimerized fatty acids, perform similarly. Liquid polysulfide polymers possessing terminal mercaptan functionality improve impact properties in conjimction with polyamine hardeners. 

Aliphatic amines are classified in primary amines (RNH2), secondary amines (R2NH), and tertiary amines (R3N), with R representing in this very general scheme an alkyl chain of any length and further functionalization. Technically interesting classes of amines are shortalkyl amines (primary, secondary, and tertiary), fatty amines, di- and polyamines, as well as aromatic amines. Table 5.3.8 highlights... 

---