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Estimation of Hydrolysis Rate Constants of Carboxylic Acid Ester and Phosphate Ester Compounds in Aqueous Systems from Molecular Structure by SPARC

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Estimation of Hydrolysis Rate Constants of Carboxylic Acid Ester and Phosphate Ester Compounds in Aqueous Systems from Molecular Structure by SPARC Estimation of Hydrolysis Rate Constants of Carboxylic Acid Ester and Phosphate Ester Compounds in Aqueous Systems from Molecular Structure by SPARC R E S E A R C H A N D D E V E L O P M E N T EPA/600/R-06/105 September 2006 Estimation of Hydrolysis Rate Constants of Carboxylic Acid Ester and Phosphate Ester Compounds in Aqueous Systems from Molecular Structure by SPARC By S. H. Hilal Ecosystems Research Division National Exposure Research Laboratory Athens, Georgia U.S. Environmental Protection Agency Office of Research and Development Washington, DC 20460 NOTICE The information in this document has been funded by the United States Environmental Protection Agency. It has been subjected to the Agency's peer and administrative review, and has been approved for publication. Mention of trade names of commercial products does not constitute endorsement or recommendation for use. ii ABSTRACT SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to calculate hydrolysis rate constants for carboxylic acid ester and phosphate ester compounds in aqueous non- aqueous and systems strictly from molecular structure. The energy differences between the initial state and the transition state for a molecule of interest are factored into internal and external mechanistic perturbation components. The internal perturbations quantify the interactions of the appended perturber (P) with the reaction center (C). These internal perturbations are factored into SPARC’s mechanistic components of electrostatic and resonance effects. External perturbations quantify the solute-solvent interactions (solvation energy) and are factored into H-bonding, field stabilization and steric effects. These models have been tested using 1471 reliable measured base, acid and general base-catalyzed carboxylic acid ester hydrolysis rate constants in water and in mixed solvent systems at different temperatures. In addition, they were tested on 397 reliably measured second order base, acid and general base-catalyzed phosphate ester hydrolysis rate constants over a range of temperatures. The RMS deviation error between predicted and measured values for carboxylic acid ester and phosphate ester compounds was close to the intralaboratory experimental error. iii EXECUTIVE SUMMARY This report is in partial fulfillment of the National Exposure Research Laboratory Task number 16386, “Developing Computational Tools for Predicting Chemical Fate, Metabolism, and Markers of Exposure”, (Goal 4 and GPRA Sub-objective 4.5.2.) under subtask title “Development of computational tools and databases for screening-level modeling of the environmental fate of toxic organic chemicals”. The primary goal of this subtask is to develop computational tools to predict the identity of chemical species to which vulnerable organisms are likely to be exposed. This screening-level model will require a chemical structure as input, and will generate a set of daughter products that can form when the chemical is released into the environment. The subtask is broadly divided into five research areas. The first area focuses on speciation of organic chemicals in aquatic systems. The second area focuses on the abiotic transformation processes hydrolysis and reduction. The third is concerned with identifying and characterizing the state variables that control the rate and extent of transformation processes in the environment. The fourth focuses on the refinement and extension of SPARC models. The area integrates 'omic tools' into environmental fate research. The primary goal of the second research area of this subtask (this project) is to develop and implement mathematical models to estimate hydrolysis rate constants of carboxylic acid esters and organophosphate ester using SPARC. This report describes the SPARC computational modeling approach to estimate hydrolysis rate constants that are necessary to predict the environmental fate of carboxylic acid ester and organophosphate ester compounds in water. The SPARC chemical reactivity models were extended to calculate hydrolysis rate constants for the aforementioned compounds in aqueous and in non-aqueous systems as a iv function of temperature in basic, acidic and neutral solution media strictly from molecular structure. The output from the hydrolysis rate constants models will inform chemists, environmentalists and toxicologists as to the chemical forms (parent or transformation products) that may be present in an ecosystem and their rates of hydrolysis transformation. The ultimate goal of this research project is to extend the SPARC solution-phase hydrolysis model to estimate the transformation rates of other chemical compounds classes of concern that may hydrolyze under environmental conditions, and to predict all possible hydrolysis pathways in aqueous and non-aqueous systems. The SPARC chemical hydrolysis models will meet some of the needs of EPA’s long term research task agenda under chemical toxicology initiative that emphasizes that EPA will have to rely heavily on predictive modeling to carry out the increasingly complex array of exposure and risk assessments necessary to develop scientifically defensible regulations. Ultimately, SPARC chemical reactivity models (ionization pKa, speciation, tautomerization, chemical hydration and chemical hydrolysis) will be integrated with the metabolic simulator TIMES (TIssue MEtabolism Simulator) and CATABOL to provide a highly reliable simulator of metabolic activity for direct application to the computational toxicology initiative. v TABLE OF CONTENTS ABSTRACT................................................................................................................................... iii EXECUTIVE SUMMARY ........................................................................................................... iv LIST OF FIGURES ..................................................................................................................... viii LIST OF TABLES ...............................................................................................................................ix 1. GENERAL INTRODUCTION ........................................................................................................1 2. QUANTITATIVE CHEMICAL THEORY .......................................................................................2 3. SPARC COMPUTATIONAL PROCEDURE...................................................................................3 4. CHEMICAL HYDROLYSIS ....................................................................................................4 4.1. Carboxylic acid Esters and Organophosphorus Hydrolysis Mechanisms and Reactions Pathway..................................................................................5 4.1.1 Carboxylic Acid Esters ................................................................................7 4.1.1.1. Base Catalyzed Hydrolysis ............................................................7 4.1.1.2. Acid Catalyzed Hydrolysis .............................................................8 4.1.1.3. General Base Catalyzed Hydrolysis................................................9 4.1.2. Phosphate ester (Organophosphorus) ................................................................9 4.1.2.1. Base Catalyzed Hydrolysis ..........................................................10 4.1.2.2. Acid Catalyzed Hydrolysis ..........................................................11 4.1.2.3. General Base Catalyzed Hydrolysis ............................................12 5. HYDROLYSIS MODELING APPROACH...................................................................................14 5.1. Reference Rate Model................................................................................................16 5.2. Internal Perturbation Models .....................................................................................16 5.2.1. Electrostatic Effect ........................................................................................17 5.2.1.1. Direct Field Effect.........................................................................18 5.2.1.2. Mesomeric Field Effect.................................................................20 5.2.1.3. Sigma Induction Effect ................................................................22 5.2.1.4. Rπ effect........................................................................................23 5.2.2. Resonance Effect ....................................................................................24 5.3. External Perturbation (Solvation Effect) Models.............................................................25 5.3.1. Hydrogen Bonding Effect........................................................................26 5.3.2. Field Stabilization Effect .........................................................................27 5.3.3. Steric Effect .............................................................................................28 5.4. Temperature Effect ....................................................................................................30 vi 6. RESULTS AND DISCUSSIONS.............................................................................................31 7. MODELS VERIFICATION AND VALIDATION..................................................................37 8. TRAINING AND MODEL PARAMETER INPUT ................................................................39 9. CONCLUSION..........................................................................................................................95
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