Tetraamine

Synthesis and Properties. A number of monomers have been used to prepare PQs and PPQs, including aromatic bis((9-diamines) and tetramines, aromatic bis(a-dicarbonyl) monomers (bisglyoxals), bis(phenyl-a-diketones) and a-ketones, bis(phenyl-a-diketones) containing amide, imide, and ester groups between the a-diketones. Significant problems encountered are that the tetraamines are carcinogenic, difficult to purify, and have poor stabihty, and the bisglyoxals require an arduous synthesis. 

An important mode of oxidation for -phenylenediamines is the formation of ben2oquinonediimines, easily obtained by oxidation with silver oxide in ether solution (17). DHmines undergo 1,4 additions with amines to generate tri- and tetraamines which readily oxidi2e in air to highly conjugated, colored products. An example of this is the formation of Bandrowski s base [20048-27-5] when -phenylenediamine is oxidi2ed with potassium ferricyanide (18). 

The tri- or tetraamine complex of copper(I), prepared by reduction of the copper(II) tetraamine complex with copper metal, is quite stable ia the absence of air. If the solution is acidified with a noncomplexiag acid, the formation of copper metal, and copper(II) ion, is immediate. If hydrochloric acid is used for the neutralization of the ammonia, the iasoluble cuprous chloride [7758-89-6], CuCl, is precipitated initially, followed by formation of the soluble ions [CuClj, [CuCl, and [CuCl as acid is iacreased ia the system. 

Tetraamination of 2,4,5,6-tetrafluoropyrimidine with dibutyl-amine involves the high reactivity of fluorine as a leaving group rather than activation by the 2,4,6-fluorines. The latter cannot account for the reactivity of the 5-fluorine since the 2,4,6-substituents undoubtedly all react first. Apparently, deactivation by the three dibutylamino groups so introduced (cf. 174) is diminished by steric hindrance to the necessary co-planarity with the ring. 

Electrocatalysis employing Co complexes as catalysts may have the complex in solution, adsorbed onto the electrode surface, or covalently bound to the electrode surface. This is exemplified with some selected examples. Cobalt(I) coordinatively unsaturated complexes of 2,2 -dipyridine promote the electrochemical oxidation of organic halides, the apparent rate constant showing a first order dependence on substrate concentration.1398,1399 Catalytic reduction of dioxygen has been observed on a glassy carbon electrode to which a cobalt(III) macrocycle tetraamine complex has been adsorbed.1400,1401... 

The choice of tridentate amine has a critical impact on the coordination mode of the ambidentate nitrite ligand, N02.499,500 Complexes with substituted tri- and tetraamines have shown that bulky substituents may prevent the formation of the -N02 bridged polymeric complexes, and the intramolecular hydrogen network may stabilize N coordination of nitrite. 

The fact that Niir tetraamine macrocycle complexes catalyze C02 electroreduction, even in aqueous solution (compare Section 6.3.4.10.2(v)), encouraged detailed studies of the interaction of... 

The first structurally characterized example of a platinum(II) derivative containing a saturated tetraamine macrocycle, 6,13-dimethyl-l,4,8,ll-tetraazacyclotetradecane-6,13-diamine has been reported (80).251 The species crystallizes as the colorless tetra-cationic complex from dilute HC104 solution by slow evaporation, where the two pendant primary amines are protonated. Other macrocyclic tetraamine complexes including [Pt([14]aneN4)]Cl2 have also been described.252... 

Comba and co-workers described a simple and efficient method for the determination of solution structures of weakly coupled binuclear copper(II) complexes.54 The technique involves the combination of molecular mechanics55,56 and EPR spectroscopy. From this standpoint they reported the structure of the complex (29). Using an acyclic tertiary tetraamine ligand, Bernhardt reported57 crystal structure of the complex (30), along with its redox properties. 

CO3 species was formed and the X-ray structure solved. It is thought that the carbonate species forms on reaction with water, which was problematic in the selected strategy, as water was produced in the formation of the dialkyl carbonates. Other problems included compound solubility and the stability of the monoalkyl carbonate complex. Van Eldik and co-workers also carried out a detailed kinetic study of the hydration of carbon dioxide and the dehydration of bicarbonate both in the presence and absence of the zinc complex of 1,5,9-triazacyclododecane (12[ane]N3). The zinc hydroxo form is shown to catalyze the hydration reaction and only the aquo complex catalyzes the dehydration of bicarbonate. Kinetic data including second order rate constants were discussed in reference to other model systems and the enzyme carbonic anhy-drase.459 The zinc complex of the tetraamine 1,4,7,10-tetraazacyclododecane (cyclen) was also studied as a catalyst for these reactions in aqueous solution and comparison of activity suggests formation of a bidentate bicarbonate intermediate inhibits the catalytic activity. Van Eldik concludes that a unidentate bicarbonate intermediate is most likely to the active species in the enzyme carbonic anhydrase.460... 

Bharadwaj synthesized the zinc complex of a mixed donor cryptand (94). The X-ray structure shows that the zinc binds in the tetraamine cavity at the base of the ligand in a tetrahedral environment and not to the oxygen donors. This demonstrates the expansion potential of the cavity compared with the free ligand.740... 

The history of dendrimer chemistry can be traced to the foundations laid down by Flory [34] over fifty years ago, particularly his studies concerning macro-molecular networks and branched polymers. More than two decades after Flory s initial groundwork (1978) Vogtle et al. [28] reported the synthesis and characterization of the first example of a cascade molecule. Michael-type addition of a primary amine to acrylonitrile (the linear monomer) afforded a tertiary amine with two arms. Subsequent reduction of the nitriles afforded a new diamine, which, upon repetition of this simple synthetic sequence, provided the desired tetraamine (1, Fig. 2) thus the advent of the iterative synthetic process and the construction of branched macromolecular architectures was at hand. Further growth of Vogtle s original dendrimer was impeded due to difficulties associated with nitrile reduction, which was later circumvented [35, 36]. This procedure eventually led to DSM s commercially available polypropylene imine) dendrimers. 

Compounds 68 have been obtained by one-pot cyclization of acyclic tetraamine 122 with ct-dicarbonyl reagents. This synthesis is not stereoselective, providing a mixture of vicinal isomers cis/trans of the bis-aminal 68 (Equation 11) <1998TL6861, 2003EJ01050, 2003T4573, 2005JOC7042>. 

A methodology described previously (Equation 11) has been successfully used to synthesize compounds 67 by intermolecular cyclization of acyclic tetraamine 137 with a-dicarbonyl reagents. This one-pot preparation furnishes... 

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