醛酮分子结构参数化表征及定量构谱关系研究

Molecular Structural Characterization and Further Quantitative Structural-Spectrum Relationships for Aldehydes and Alkanones

应用定量结构谱学性质相关(QSSR)方法研究脂肪醛酮谱学性质与分子描述符之间的定量关系.采用DRAGON 5.4软件和HyerChem 7计算了脂肪醛酮分子的258种结构类参数和12种量子化学参数.根据偏差权重法筛选出24种结构描述符.采用多元逐步回归分析建立了14种脂肪酮结构-紫外最大吸收波长关系,得到最佳方程:λmax=261.452+5.318X2V+1.109(ELUMO-EHOMO).方程相关系数R为0.984,标准偏差S为1.1722.另一个8种脂肪醛酮结构-羰基红外伸缩振动频率定量关系为:v=1726.082-4.823EHOMO+2.2591×10-4ET.相关系数R为0.991,标准偏差S为1.863."逐一剔除"交叉验证的结果证明,两个模型具有良好的稳定性和较强的预测能力.参数物理意义及对谱学性质影响的深入分析表明,其中的结构参数X2V是影响脂肪酮紫外最大吸收波长的关键因素,而量化参数(ELUMO-EHOMO)也是一个不可忽视的因素.量子化学参数ET和EHOMO是影响脂肪醛酮羰基红外伸缩振动频率的主要因素.

Quantitative structure-spectrum relationship（QSSR） method was performed to study the re- lationship between spectral properties and molecular descriptors of Aldehydes and Alkanones. With the DRAGONS. 4 software and HyerChem7, 258 structural parameters and 12 quantum chemistry parameters for Aldehydes and Alkanones are calculated. 24 structural descriptors are chosen by using the variable se- lection method of weighted deviation. A quantitative relationship study between the structure and UV max- imum absorption wavelength λmax of 14 sorts of Alkanones is set up with stepwise regress kmox=261. 452＋ 5. 318 X2Vq-1. 109（ELuMo--EnoMO）. where R and S are 0. 984 and 1. 1722 respectively. Another quantita- tive relationship study between the structure and Infrared stretching vibration frequency v of carbonyl of 8 sorts of Aldehydes and Alkanones is set up with stepwise regress v= 1726. 082--4. 823E^oMo ＋2. 2591 X 10-4ET. where R and S are 0. 991 and 1. 863 respectively. Furthermore,leave-one-out cross validation as performed, which confirmed the good stability and powerful prediction of two model. The physical meaning and the influence of the prameters on UV maximum absorption wavelength and Infrared stretching vibra- tion frequency of Aldehydes and Alkanones were investigated. Structural parameter X2V is the key factor affecting UV maximum absorption wavelength of Alkanones and quantum chemistry parameter （ELuMO- E^OMO） can not be ignoreed. Quantum chemistry parameter ET and EHOMO are main factors affecting Infrared stretching vibration frequency of Aldehydes and Alkanones.