脂肪胺、醛、醇、酸、醚气相碱性与分子结构之间定量关系的拓扑化学研究  

Studies on the Quantitative Relation Between Molecular Structure and Gas Phase Basicity of Aliphatic Amine, Alcohol, Ether and Aldehyde Using Topological Method

作　　者：王克强[1] 

机构地区：[1]洛阳师范学院化学系,河南洛阳4710022

出　　处：《洛阳师范学院学报》2003年第5期42-46,共5页Journal of Luoyang Normal University

摘　　要：根据化学热力学原理和量子力学原理,用拓扑方法探讨了脂肪胺、醛、醇、酸、醚的气相碱性与其分子结构之间的定量关系,发现气相碱性的大小主要取决于分子中亲合基团的特性和烷基基团的种类、数目和烷基基团与亲合基团之间的距离,据此提出了一种能够合理表征脂肪胺、醛、醇、酸、醚的气相碱性(PA)与分子结构之间的定量关系式 PA=251.1886[PA(G)+∑∑B_i(4-v_j)n_j^(i)]^(1/5)式中 PA(G)是与亲合基因特性有关的常数,n_j^(i)(i,j=1,2,3,4)为i级烷基基因j的数目,v_j为烷基基因j的顶点度,B_1=17.4546,B_2=17.5552,B_3=10.5896,B_4=5.5842,PA(-NH_2)=530.84,PA(-NH-)=576.14,PA(-N<)=592.79,PA(-O-)=224.27,PA(-OH)=207.11,PA(-COOH)=263.90,PA(-CHO)=242.11,PA(-HCOO)=280.04.对73种化合物气相碱性的计算结果表明,计算值与实验值的一致性令人满意,平均误差0.335％.Based on the thermodynamics and quantum mechanics, the relation between molecular structure and gas basicity of aliphatic amine, alcohol, ether and aldehyde was studied by means of topological method, and a quantitative relation formula was developed to predict the gas basicity PA where the PA( G) was function of the property of affinity group G, n, ( i ,j - 1,2,3,4) )were the number of the ith order group j, vj was the degree of vertex (alkyl group) j. B1 = 17.4546, B2=17.5552, B3 =10.5896, B4 =5.5842,PA(-NH2)=530.84,PA(-NH-)=576.14,PA(-N<)=592.79,PA(-O-)= 224.27, PA(-OH) = 207.11, PA(-COOH)=263.90,PA(-CHO)=242.11,PA(-HCOO)= 280.04. The results showed that the calculated values of gas basicity were in good agreement with the experimental data. The mean relative deviation was 0.335% for 73 aliphatic amine, alcohol, ether and aldehyde.

关 键 词：气相碱性 亲合基团 结构性能关系 脂肪胺 脂肪醇 脂肪醚 脂肪醛 脂肪酸 

分 类 号：O621.2[理学—有机化学]