Iowa State University Capstones, Theses and Graduate Theses and Dissertations Dissertations 2016 Synthesis of triacetic acid lactone Mannich bases and their inhibition of corrosion John Rey Apostol Romal Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/etd Part of the Chemistry Commons Recommended Citation Romal, John Rey Apostol, "Synthesis of triacetic acid lactone Mannich bases and their inhibition of corrosion" (2016). Graduate Theses and Dissertations. 15802. https://lib.dr.iastate.edu/etd/15802 This Thesis is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Synthesis of triacetic acid lactone Mannich bases and their inhibition of corrosion by John Rey Apostol Romal A thesis submitted to the graduate faculty in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Major: Organic Chemistry Program of Study Committee: George A. Kraus, Major Professor Brent Shanks Arthur Winter Iowa State University Ames, Iowa 2016 Copyright © John Rey Apostol Romal, 2016. All rights reserved. ii DEDICATION To my family and friends. iii TABLE OF CONTENTS DEDICATION ........................................................................................................... ii LIST OF ABBREVIATIONS .................................................................................... iv ACKNOWLEDGEMENTS ....................................................................................... vi ABSTRACT………………………………. .............................................................. viii CHAPTER I. MANNICH REACTIONS OF THE BIO-BASED TRIACETIC ACID LACTONE .......................................................................... 1 1.1. Introduction .............................................................................. 1 1.2. Results and Discussion ............................................................ 19 1.3. Conclusion ............................................................................... 33 1.4. Experimental ............................................................................ 33 1.5. References ................................................................................ 45 CHAPTER II. CORROSION INHIBITION OF SMALL ORGANIC MOLECULES AND TRIACETIC ACID LACTONE MANNICH BASES ............................................................................................ 49 2.1. Introduction .............................................................................. 49 2.2. Results and Discussion ............................................................ 63 2.3. Conclusion ............................................................................... 73 2.4. Experimental ............................................................................ 74 2.5. References ................................................................................ 77 CHAPTER III. GENERAL CONCLUSIONS…………………………………….. 80 iv LIST OF ABBREVIATIONS ACAT acyl-CoA cholesterol acyltransferase AcOH acetic acid CDCl3 deuterated chloroform Cu NP copper nanoparticle DCE dichloroethane DHA dehydroacetic acid DMAD dimethylacetylenedicarboxylate DMM dimethoxymethane DMSO dimethylsulfoxide EA ethyl acetate E. Coli Escherichia coli EDG electron-donating group EG ethylene glycol EI electron ionization ESI electronspray ionization EWG electron-withdrawing group FDCA 2,5-furandicarboxylic acid GC gas chromatography HMF 5-hydroxymethylfurfural ICP Inductively Coupled Plasma IE inhibition efficiency v LRMS low resolution mass spectrometry MCR multicomponent reaction MeCN acetonitrile MHz megahertz mM millimolar MS mass spectrometry NMR Nuclear Magnetic Resonance OCV open circuit voltage PEF polyethylene furanoate PEIS Potentiostatic Electron Impedance Spectroscopy PET polyethylene terephthalate ppm parts per million QTOF quadruple time of flight TAL triacetic acid lactone TLC thin-layer chromatography THF tetrahydrofuran UV ultraviolet vi ACKNOWLEDGEMENTS I am grateful for the opportunity of working under the supervision of Dr. George Kraus. There have been many times I feel challenged conducting research in his lab, but with his motivation and passion for mentoring I was able to comprehend. I will always appreciate his patience and understanding. His dedication and excellence in synthetic organic chemistry will always serve as an inspiration. I would like to express my gratitude to my graduate committee members: Dr. Brent Shanks and Dr. Arthur Winter for their time and support throughout my stay in Iowa State University. Their opinions and advices were greatly appreciated. I acknowledge Dr. Wenzhen Li, his student Yang Qiu, and the rest of present Li’s group members for the opportunity to work in the field of electrochemistry. I would also like to recognize Dr. Wenyu Huang and his group for providing me the experience working in the field of catalysis during the first two semesters of my graduate studies. The computational efforts of Logan Fischer and Shinae Kim were also appreciated. I feel delighted working in Kraus lab in the presence of my motivating colleagues: Dr. Uma Wanninayake, Dr. Pengfei Dong, Yang Qu, Ivan Geraskin, and Huangchao Yu. Their motivation and support towards the completion of my Masters of Science study were very much highly appreciated. All the intellectual and personal life discussions will always be cherished. I would especially thank Aaron Zoellner for the great brotherhood he has imparted me. Through my ups and downs in the past year, he has been there to celebrate with and an anchor providing me with great advices and motivation. His unconditional friendship vii will always be treasured. I also want to express my heartfelt appreciation to Dr. Michelle Thompson, Hannah Crotty, and Miles Arthur White for all the motivation, suggestions, and advices they have provided me about research and personal struggles. They have always made themselves available if I need them the most. I am also grateful to Fritzie Rivas, Dr. Kristin Manibog, Mapi Faylon, Katrina Lutap, and Darlene Sanchez for bestowing me with their sisterly-love since I moved in to Ames. The companionship of Eric Schultz, Fitim Kelmendi, Peter Spurgeon, Ming-Hsun Cheng, Charles Nyamekye, and Frank Hanes were also greatly acknowledged. Finally, I would want to express my heartfelt thanks and dedication of this success to my parents Joy and Rey Romal for their sacrifices and unconditional love they have given me my entire life. They have not only provided me with the necessities of life, but they also have endowed me with the luxury of it. They have nurtured me to be resilient, hardworking, and patient. I would also want to dedicate this work to my extended family that have always shown me their love and support towards my graduate studies. viii ABSTRACT Our society has relied mostly on fossil-based materials as source of carbon for industrially important chemicals. The non-renewability of this petroleum-based material, however, requires an alternative for sustainability. Presently, there has already been great advancement in utilizing biomass as a renewable carbon source. Triacetic acid lactone (TAL) has been explored as a potential renewable platform chemical by the Center for Biorenewable Chemicals (CBiRC). In the presence of microbial and enzymatic biocatalysts, TAL can be biosynthesized from glucose. Subsequently, TAL can be transformed to variety of high-valued commodity chemicals using chemical catalysts. In Chapter 1 of this work, an efficient method was developed to utilize TAL in the 3-components Mannich reaction. This multi-component reaction is an efficient way of making highly-functionalized molecules. The participation of TAL as the enolizable component in the Mannich reaction has not been well studied in the literature. The successful production of Mannich bases containing TAL moiety demonstrates the versatility of TAL as a platform chemical. In Chapter 2, the corrosion inhibition activity of 2-pyrones, pyridines, and TAL- derived Mannich bases in mild steel was evaluated. There already exist organic molecules corrosion inhibitors. Some TAL-based molecules and pyridines, however, have not been very well known for this application. This chapter gives an overview of other potential small organic molecule corrosion inhibitors. Structure similarity with the previously studied, opuntiol, is the basis for evaluating the efficiency of these molecules. Further studies are still needed to compare the activity of these organic molecules with the corrosion inhibitors used in the industry. ix ~ To God be the glory ~ 1 CHAPTER I MANNICH REACTIONS OF THE BIO-BASED TRIACETIC ACID LACTONE 1.1 Introduction 1.1.1 Progress to bio-based platform chemicals Presently, numerous industries from plastics, textiles, and cosmetics, to polymers, pharmaceuticals, and fuel rely on petroleum-based chemicals as one of the raw materials for production. The gradual depletion of fossil-based resources poses a concern to these chemical industries. In addition to this, the risk in coal mining and the generation of environmentally harmful by-products are also factors to seek an alternative for the production of energy. As a result, several efforts have been made to resolve this issue. Many believe that the most feasible solution is