Development of Simple QSPR Models for the Prediction of the Heat of Decomposition of Organic Peroxides

Abstract

Quantitative structure-property relationships represent alternative method to experiments to access the estimation of physico-chemical properties of chemicals for screening purpose at R&D level but also to gather missing data in regulatory context. In particular, such predictions were encouraged by the REACH regulation for the collection of data, provided that they are developed respecting the rigorous principles of validation proposed by OECD. In this context, a series of organic peroxides, unstable chemicals which can easily decompose and may lead to explosion, were investigated to develop simple QSPR models that can be used in a regulatory framework. Only constitutional and topological descriptors were employed to achieve QSPR models predicting the heat of decomposition, which could be used without any time consuming preliminary structure calculations at quantum chemical level. To validate the models, the original experimental dataset was divided into a training and a validation set according to two methods of partitioning, one based on the property value and the other based on the structure of the molecules by the mean of PCA. Four QSPR models were developed upon the type of descriptors and the methods of partitioning. The 2 models issuing from the PCA based method were highlighted as they presented good predictive power and they are easier to apply than our previous quantum chemical based model, since they do not need any preliminary calculations.

Chemoinformatics for the Safety of Energetic and Reactive Materials at Ineris

“…Performances of the quantum chemical based models developed for the impact sensitivities of nitrocompounds. [59] Target Compounds R Models on the hazardous properties of organic peroxides were developed within the PREDIMOL project (2010-2014), [21,66] which aimed to evidence the potential of molecular-scale modeling for the prediction of physicochemical properties in the framework of the European REACH regulation. [9] Organic peroxides are defined by the presence of unstable OÀ O bonds in the molecule (as shown in Figure 2).…”

Perylene-Based Smart Fluoroprobe with Dual Function: Ratiometric Response toward Hazardous Organic Peroxides and Pure White Light Generation via Self-Assembly

“…On the other hand, organic peroxides (OPs) are widely used as an oxidizing agent and can be used as a catalyst and as free radical initiators for chain polymerization reactions. , However, OPs are among the most hazardous substances handled in the lab due to their high instability, reactivity, and sensitivity to external factors such as heat, light, and pressure. , They also pose severe adverse effects on human health, including phototoxic and cytotoxic effects and irritation of the skin and the mucous membrane. In a chemical laboratory, most commonly used ethereal solvents, like tetrahydrofuran (THF), 1,4-dioxane, and diethyl ether, can generate an elevated amount of hazardous OPs over time via auto-oxidation in the presence of oxygen and light. − The α-hydrogen to oxygen in the ethereal solvents can be easily abstracted by a radical initiator, which subsequently generates OPs via auto-oxidation. ,, These ethereal solvents containing elevated amounts of OPs can sometimes interfere with the measurement of interest and give undesirable byproducts in radical chain reactions.…”

First QSPR models to predict the thermal stability of potential self-reactive substances

“…Recent reviews [15][16][17][18] well illustrated the success of application of this approach for physical hazards and process safety issues. For instance, models were developed for the thermal decomposition properties of nitro compounds [19][20][21] or organic peroxides [22][23][24][25][26][27]. Unfortunately, no QSPR model dedicated to self-reactive substances has been developed to date, probably due to the lack of experimental data.…”