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本文提出计算芘系芳烃共振能的苯环计数(BRC)公式,并结合母子加和(PPC)公式共计算了34个芘系烃的共振能。结果表明,芘系的BRC公式对省系的BRC公式有继承性。包括芘系在内的91个芳烃的REPE_(BRC),和REPE_(BRC-PPC)与第一电离势能IP_1之间仍保持较好的线性关系,r=0.9405(91),S=0.1453。56个芳烃的△RE_(BRC)和△RE_(BRC-PPC)与Diels-Alder反应的二级速度常数的对数之间也保持良好的线性相关性,r=0.9612(56),S=0.4622。前文应用苯环计数(BRC)公式[公式(1),式中N为分子苯环总数,m为主链的环数,n、o、p和q分别是第一、第二、第三及第四侧链的环数,i为交叉点数]及母子加和(PPC)公式[公式(2),式中PRE为分子母体共振能(第一母体共振能),RE_Ki为已知结构共振能,PRE_i为已知结构母体共振能(第二母体共振能)],共计算了90个稠环芳烃的共振能。但公式(1)不适用于π电子数等于4n的芘系烃。在分析对照3,4—省并芘类和线省苯环数和结构计数(SC)的数量关系基础上,我们将公式(1)演变成专门计算芘系稠环烃共振能的BRC公式,从而扩大了苯环计数法的应用。
In this paper, the formula of calculating the benzene ring counting (BRC) for the resonance energy of pyrene aromatics is proposed, and the resonance energies of 34 pyrene hydrocarbons are calculated with the formula of mother-daughter addition (PPC). The results show that the pyrene BRC formula inherits the provincial BRC formula. REPE_ (BRC) of 91 aromatics, including pyrene, and REPE_ (BRC-PPC) maintained a good linear relationship with the first ionization potential IP_1, r = 0.9405 (91), S = 0.1453.56 There was also a good linear correlation between △ RE BRC and △ RE BRC PPC of aromatic compounds and the logarithm of the second order velocity constant of Diels-Alder reaction, r = 0.9612 (56) and S = 0.4622. In the above, the formula of benzene ring count (BRC) is used [formula (1), where N is the total number of benzene rings in the molecule, m is the number of rings in the main chain, n, o, p and q are the first, second, The number of rings of the fourth side chain, i is the number of intersections], and the formula of parent-child summation (PPC) [formula (2)] where PRE is the molecular parent resonance energy (first parent resonance energy), RE_Ki is the known structure resonance energy , PRE_i is the resonance energy of the parent structure of the known structure (the second parent resonance energy)], and the resonance energies of 90 condensed aromatic hydrocarbons are calculated. However, equation (1) does not apply to pyrene-based hydrocarbons with π electrons equal to 4n. Based on the analysis of the relationship between the number of 3,4-and-pyrene and the number of benzene rings and the number of structures (SC) in the control, we formulate (1) into a BRC formula that specializes in the resonance energy of pyrene- Thus expanding the application of the benzene ring counting method.