Nitrogen bases basicity

Amines are ammonia derivatives in which one or more hydrogen atoms have been replaced by an organic radical. Amines are sometimes called nitrogen bases. Basic chemistries include fatty amines (as primary, secondary, tertiary, and polyamines), amine salts, quaternary ammonium compounds, amine oxides, and amides. 

Methylation of nitrogen at the 2 position also proves to be consistent with diuretic activity. Condensation of 160 with urea affords the heterocycle, 193. Treatment of this compound with methyl iodide and base effects alkylation on the more acidic ring nitrogen (194). Basic hydrolysis then gives the N-methylated aminosulfonamide (195). Condensation of this with chloroacetalde-... 

The nucleic acids, deoxyribonucleic acid (DNA) and ribonucleic acid (RNA), which carry embedded in their complex molecules the genetic information that characterizes every organism, are found in virtually all living cells. Their molecules are very large and complex biopolymers made up basically of monomeric units known as nucleotides. Thus DNA and RNA are said to be polynucleotides. The nucleotides are made up of three bonded (linked) components a sugar, a nitrogenous base, and one or more phosphate groups ... 

The initiating nucleophile in the vast majority of these studies is the hydroxide anion. However, in principle, any nucleophile can add to the keto or formyl group to give rise to an anionic intermediate, which then could act as an intramolecular nucleophile and effect hydrolysis of the ester. Their relative effectiveness will depend on two factors the relative extent of formation and the nucleophilicity of the adduct. The nucleophiles that have been investigated are hydroxide, cyanide, morpholine and piperazine. The only quantitative comparison available is that of hydroxide, morpholine and piperazine, which are effective in the order of ca. 102 10-3 1 (Bender et al., 1965 Dahlgren and Schell, 1967). For morpholine and piperazine this is as expected on the basis of their relative basicities. However, the expected order of increasing formation of the adducts would be cyanide > nitrogen bases > hydroxide (Hine, 1971). At this time, these results cannot be analysed further, but more work on the systems could enable the structural dependence and reactivity to be elucidated. 

Alkaloids are found mainly in plants, and are nitrogenous bases, typically primary, secondary, or tertiary amines. The basic properties facilitate their isolation and purification. Water-soluble salts are formed in the presence of mineral acids (see Section 4.11.1), and this allows separation of the alkaloids from any other compounds that are neutral or acidic. It is a simple matter to take a plant extract in a water-immiscible organic solvent, and to extract this solution with aqueous acid. Salts of the alkaloids are formed, and, being water soluble, these transfer to the aqueous acid phase. On basifying the acid phase, the alkaloids revert back to an uncharged form, and may be extracted into fresh organic solvent. 

The pKj of the basic nitrogen of dorzolamide is very temperature-dependent, and the nitrogenous base becomes weaker as the temperature increases. Consequently, the measured pH of any given solution will vary with temperature. As illustrated in Figure 5, an increase in pH with decreasing temperature is accompanied by a change in the free base concentration. 

A comparison of calculated and measured proton affinities (basicities) of nitrogen bases relative to the proton affinity of ammonia as a standard is provided in Table 6-17. The calculations correspond to the usual theoretical models, and the experimental data derive from equilibrium measurements in the gas phase. The data span a large range the proton affinity of the strongest base examined, quinuclidine, is some 27 kcal/mol greater than that of the weakest base, ammonia. 

Nucleophilicity. A distinction is usually made between nucleophilicity and Lowry-Bronsted basicity [213]. The latter involves specifically reaction at a proton which is complexed to a Lewis base (usually H2O), while the former refers to reactivity at centers other than H. Linear correlations have been shown for gas-phase basicity (proton affinity) and nucleophilicity of nitrogen bases toward CH3I in solution [214] where the solvent is not strongly involved in charge dispersal. In each case, reaction of the base/nucleophile... 

The basic ionization of nitrobenzene in sulphuric acid was investigated cryoscopically by Treffers and Hammett 12], who found that nitrobenzene, unlike many oxygen and nitrogen bases, is incompletely... 

In the gas phase, (3-lactams are weaker bases than acyclic amides. Ab initio calculations show that (3-lactams are oxygen bases, but the gap between the oxygen and nitrogen intrinsic basicities is much smaller than in normal amides, a result of redistribution due to hybridization changes (92JA4728). 

The basicity of amines is a function of the hybridization of the nitrogen atom.59 The more electronegative the nitrogen atom, the less readily it will share its kme pair electrons and act as a base. The series of nitrogen bases, aliphatic attunes, pyridine, and nitriles, exhibits this property ... 

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