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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Structure-activity relationship for the addition of OH to (poly)alkenes: Site-specific and total rate constants
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Structure-activity relationship for the addition of OH to (poly)alkenes: Site-specific and total rate constants

机译：在（聚）烯烃中添加OH的结构-活性关系：特定位置和总速率常数

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摘要

A novel site-specific structure-activity relationship was developed for the site-specific addition of OH radicals to (poly)alkenes at 298 K. From a detailed structure-activity analysis of some 65 known OH + alkene and diene reactions, it appears that the total rate constant for this reaction class can be closely approximated by a sum of independent partial rate constants, k(i), for addition to the specific (double-bonded) C atoms that depend only on the stability type of the ensuing radical (primary, secondary, etc.), that is, on the number of substituents on the neighboring C atom in the double bond. The (nine) independent partial rate constants, k(i), were derived, and the predicted rate constants (k(OH,pred) = Sigma k(i)) were compared with experimental k(OH,exp) values. For noncyclic (poly)alkenes, including conjugated structures, the agreement is excellent (Delta < 10%). The SAR-predicted rate constants for cyclic (poly)alkenes are in general also within < 15% of the experimental value. On the basis of this SAR, it is possible to predict the site-specific rate constants for (poly)alkene + OH reactions accurately, including larger biogenic compounds such as isoprene and terpenes. An important section is devoted to the rigorous experimental validation of the SAR predictions against direct measurements of the site-specific addition contributions within the alkene, for monoalkenes as well as conjugated alkenes. The measured site specificities are within 10-15% of the SAR predictions.
机译：开发了一种新颖的位点特异性结构-活性关系，用于在298 K下向（聚）烯烃位点特异性添加OH自由基。通过对约65种已知的OH +烯烃和二烯反应的详细结构活性分析，看来对于该反应类别的总速率常数，可以通过独立的部分速率常数k（i）的总和来近似估算，以添加到仅取决于随后基团的稳定性类型的特定（双键）C原子上（伯，仲等），即双键中相邻C原子上的取代基数目。导出了（九个）独立的部分速率常数k（i），并将预测的速率常数（k（OH，pred）= Sigma k（i））与实验性k（OH，exp）值进行了比较。对于包括共轭结构在内的非环状（聚）烯烃，其一致性极好（Delta <10％）。环状（聚）烯烃的SAR预测速率常数通常也小于实验值的15％。基于该SAR，可以准确预测（聚）烯烃+ OH反应的位点速率常数，包括较大的生物化合物，例如异戊二烯和萜烯。一个重要的部分专门针对单烯烃和共轭烯烃对SAR预测的严格实验验证，以直接测量烯烃中特定于位点的加成贡献。测得的位点特异性在SAR预测值的10-15％之内。

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