Pyrimidine, aromaticity estimates

Magnetic susceptibility anisotropy has been used for the estimation of relative aromaticity of some azines in comparison with benzene (77JCS(P2)897). If the extent of ir-electron delocalization for benzene is taken as 1.0, the corresponding values for azines are pyridine 0.7, pyridazine 0.7, pyrimidine 0.5, and 1,3,5-triazine 0.3. 

Magnetic susceptibility anisotropy has been used to estimate relative aromaticities of some azines <1977JOC897>. If the extent of -electron delocalization for benzene is taken as 1.0, the corresponding values for azines are pyridine 0.7, pyridazine 0.7, pyrimidine 0.5, and 1,3,5-triazine 0.3. Another quantitative magnetic index is the exaltation of the total magnetic susceptibility (A). All aromatic systems reveal large A values, whereas for nonaromatic compounds A is close to zero and it is assumed that aromaticity increases with A. For six-membered monocycles the following values of A have been reported (in units of cm3 mol-1 x —106) benzene (17.9), pyridine (18.3), pyridazine (8.7), pyrimidine (18.2), pyrazine (12.7), l-ethyl-2-pyridone (13.0), and 1,3,5-triazine (19.0). 

The electron affinities (EA) of the nucleobases have not been determined experimentally. Calculated values for the vertical and adiabatic EA obtained by scaling experimental and calculated values for other aromatic molecules are summarized in Table 1 [33a]. The vertical values follow the order U>T>C>A>G, with U having the largest (most positive) EA. The calculated adiabatic EA for C is less positive than the values for T or U. Chen and Chen [36] have asserted that the electron affinities of the purines are larger than those of the pyrimidines. However, this claim appears to be based upon questionable reduction potential measurements (see p. 114). The nucleobase anion radicals are estimated to be stabilized by c. 3 eV in aqueous solution. 

Local MP2-based method for estimation of intermolecular interactions in aromatic molecules. Benzene, naphthalene, and pyrimidine dimers. A comparison with canonical MP2 method75... 

In 1975 the anion of T was observed in a mass spectrometer, indicating a positive valence-state Ea for T. In 1990 the Ea of AGCUT were predicted using substitution, replacement, and conjugation effects [10-14], In order to estimate the Ea of substituted compounds, that of the parent compounds is required. In 1974 I. Nenner and G. J. Schulz estimated the AEa of quinoline (0.36 eV), pyradazine (0.40 eV), pyrimidine (0.00 eV), pyrazine (0.40 eV), and s-triazine (0.45 eV) from electron transmission spectra and half-wave reduction potentials [15]. No adiabatic electron affinities of aromatic nitrogen heterocyclic compounds were measured in the gas phase before 1989 [16]. 

In 1990 the AEa for C, U, and T were predicted to range from 0.6 eV to 0.75 eV, while the AEa of A and G were predicted to be higher. These estimates were based on an Ea of 0.3 eV for pyrimidine and the observation that C, U, and T are hydroxyl-, methyl-, and amino-substituted pyrimidines. From the data for pairs of molecules shown in Table 12.1, quantitative measures of the substitution, conjugation, and replacement effects were postulated. The replacement of a CH by N in an aromatic system increases the Ea by 0.2 eV to 0.8 eV. The substitution of a hydroxyl... 

Table 5,3 Examples of QSAR models for estimating toxicity to fish of non-polar non-specific toxicants (e.g. alkanes, alkenes, saturated and unsaturated halogenated aliphatic hydrocarbons, basic ethers, cyclic ethers, ketones, amides, secondary and tertiary aliphatic and aromatic amines, alkylbenzenes, halogenated benzenes, piperazines, pyrimidines, polychlorinated hydrocarbon pesticides) log LC50 correlations with various parameters. 

Local MP2-Based Method for Estimation of Intermolecular Interactions in Aromatic Molecules. Benzene, Naphthalene, and Pyrimidine Dimers. A Comparison with Canonical MP2 Method. 

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