Macrocycle formation through carbon acid-formaldehyde condensation reactions of bis(propane-1,2-diamine)- and bis (2-methylpropane-1,2-diamine)-copper(II) ions

The reaction of the bis(1,2-diamine) copper(II) complexes of racemic propane-1,2-diamine (pn) and 2-methylpropane-1,2-diamine (dmen) with formaldehyde and nitroethane in methanol under basic conditions yields minor macrocyclic condensation products in addition to the major acyclic products. Where C-pendant methyl groups on the pair of coordinated diamines are in cis dispositions, the first -NH-CH2-C(CH3)(NO2)-CH2-NH- ring formation occurs at amine pairs distant from these C-methyl substituents, and further reaction to yield a macrocycle is not observed. However, where the C-methyl substituents are in trans dispositions, the chemistry proceeds to yield the macrocycle. Commencing with pn, trans-(6,13-diammonio-2,6,9,13-tetramethyl-1,4,7,10-tetraazacyclotetradecane)copper(II) perchlorate formed and crystallized in the space group P2(1)/n, with a 9.782(2), b 9.2794(6), c 17.017(4) Angstrom, beta 103.24(1)degrees. The copper ion is found in a square-planar environment, with the two methyl groups of the pn residues and the pairs of introduced pendant groups all in trans arrangements.

Slaking, dispersion, and crust formation

Soil structure is generally defined as the arrangement, orientation, and organization of the primary particles of sand, silt, and clay into compound aggregates, which exhibit properties that are unequal to the properties of a mass of nonaggregated material with a similar texture.6 Therefore the nature of soil structure is that it conveys specific properties to the soil and any alteration, i.e., breakdown or structural development, to the soil structural units will affect the physical properties of the soil. The aggregation and organization of the soil particles tend to form a hierarchical order4, 5 where the lower orders tend to have higher densities and greater internal strength than the higher orders. A schematic diagram of the hierarchical nature of soil structural elements in a clay soil is given in Fig. 1.4 Clay particles tend to form domains (packets of parallel clay sheets, generally consisting of 5-7 sheets), in turn several domains form clusters, followed by several orders of clusters, micro- and macroaggregates. The hierarchical nature implies that the destruction of a lower order will result in the destruction of all higher hierarchical orders. An example is the dispersion of sodic clay domains which results in the destruction of all higher orders, resulting in a dense soil with low hydraulic conductivity. Hence the clay domains are the fundamental building blocks of the soil and its integrity may determine the soil's physical properties and behavior.