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Oxidative Chemistry of Phosphorothionate And (i). OXIDATIVE CHEMISTRY OF PHOSPHOROTHIONATE AND RELATED COMPOUNDS A thesis submitted in fulfilment of the requirement for the degree of Doctor of Philosophy from Department of Organic Chemistry School of Chemistry University of New South Wales by Jeong Han Kim March 1992 (ii) DECLARATION This is to certify that the work described in this thesis was carried out by the author during the period March 1988 to March 1992, in Department of Organic Chemistry, University of New South Wales, Australia under the supervision of Dr. Robert F. Toia and Associate Professor Michael J. Gallagher. It is hereby declared that this thesis has not been submitted in part or in full to any other university or institution for the any degree or diploma. Date: .l.$:;.J.... ~.t't.~. (iii) ACKNOWLEDGEMENTS I would like to express my deepest gratitude and appreciation to my supervisors, Dr. Robert F. Toia and Associate Professor Michael J. Gallagher for their help, guidance and continuous encouragement throughout the study. My special thanks also go to Professor J. E. Casida for the valuable extensive study in Pesticide Chemistry and Toxicology Laboratory in U. C. Berkeley and to Professor C. K. Park in Seoul National University for his guidance and encouragement. Many thanks also to Dr. J. Hook for his great help with 3lp NMR, to the staff members of the Department of Organic Chemistry in University of New South Wales and to my fellow students for their help and friendship. Great acknowledgement is made to the Australian government for financial support in the form of a Commonwealth Postgraduates Research A wards. I would like to express my appreciation and love to my dear wife, family and relatives for their patience, encouragement and support. (iv) ABSTRACT The oxidation of cyclic phosphorothioates has been studied to investigate the stereochemical changes which occur during the oxidatively - induced displacement reactions. The stereochemistry of the starting materials, i.e. cis- and trans-5- hydroxymethyl-5-methyl-2-thiono-r-2-ethoxy-1,3,2-dioxaphosphorinane was confirmed by single crystal X-ray crystallography of their acetate and 3,5-dinitro benzoate derivatives, respectively. All of the oxidation studies were carried out with varying molar ratio of MCPBA n (m-chloroperbroic acid) to substrate and variety of solvents were used. Product formation on oxidation of the above cis- and trans- isomers in CDCl3 occur with substantial retention of configuration. With 1-methyl-4-phospha-3,5,8-trioxabicyclo [2,2,2] octane-4-sulfide (BPS) only 1-methyl-4-phospha-3,5,8-trioxabicyclo [2,2,2] octane-4-oxide (BPO) was obtained. In CH30H, however, both isomers and BPS reacted similarly to give the cis- and trans-methyl phosphates by non stereospecific phosphorylation of methanol. The major intermediate noted during the oxidation was extensively studied by spectroscopic methods and assigned as the monocyclic sulfenate. Minor products and non-phosphorus products were also assigned by MS and GC-MS studies. In aqueous acetone, an acyclic hydrogenphosphonate was commonly observed from both isomers and BPS. With 5,5-dimethyl dioxaphosphorinanes as comparison compounds, it was found that the hydroxyl group of the cis- and trans- isomers does not affect the overall reaction in CH30H although it may play a role in stabilizing the intermediates. From model studies with acyclic phosphorothioates, disulfides were found as phosphorylating intermediates in CH30H. Using an 180-containing thiolate as the starting material the mechanistic pathway was investigated in the formation of the methyl (v) ester from oxidation in CH30H and it appeared that product fonnation proceded via a rearragement process. In an attempted synthesis of the major intennediates by the reaction between cis­ trans- isomers and S(hCh only BPO was obtained. Furthe(more the reaction between BPS and S(hCh yielded trans-monocyclic chloridate which was confirmed by X-ray analysis and the mechanistic details of their reaction were postulated. In the alcoholyses of BPO and BPS stereospecific ring opening to the trans­ isomer was observed at early stage and this was confirmed by X-ray analysis. It was also shown that the trans- and' cis- isomers equilibrated through the intermediate acyclic derivatives. (vi) ABBREVIATIONS BPO 1-Methyl-4-phospha-3,5,8-trioxabicyclo [2,2,2] octane-4-oxide BPS 1-Methyl-4-phospha-3,5,8-trioxabicyclo [2,2,2] octane-4-sulfide MCBA m-Chlorobenzoic acid MCPBA m-Chloroperbenzoic acid MIBO 2-Methylthio-4H-1,3,2-benzodioxaphosphorin-2-oxide 1MP Trimethyl phosphite TMPO Trimethyl phosphate 1MPS Trimethyl phosphorothionate (vii) TABLE OF CONTENTS Title page i Declaration 11 Acknowledgements iii Abstract iv Abbreviations vi Table of Contents Vll Introduction 1 Results and Discussion Syntheses of Cyclic phosphorothioates and related compounds. 35 Structural assigment of the isomers of dioxaphosphorinanes 41 Oxidation of cis- and trans-5-hydroxymethyl-5-methyl-2-thiono-r- 2-ethoxy-1,3,2-dioxaphosphorinane [cis- and trans-(116)] by MCPBA. 58 Oxidation of BPS by MCPBA. 77 Oxidation of 5,5-dimethyl-2-thiono-2-ethoxy-1,3,2 -dioxaphosphorinane ( 133). 86 Spectroscopic investigation of the intermediate E in the oxidation of BPS by MCPBA in CD3OD (CH3OH). 88 Oxidation of Triethyl phosphorothionate (TEPS) and trimethyl phosphorothionate (TMPS) 105 (viii) Oxidation of the sulfenate (EtO)iP(O)SOCH3 (146) by MCPBA 112 Reaction of trimethyl phosphite (TMP) with Bis(diethoxy phosphinyl) ·disulfide. 114 Oxidation of bis(diethyl phosphinyl)disulfide (130) by MCPBA. 115 Oxidation of Q,Q-diethyl-S-phenyl phosphorothiolate-1SO (lSO-thiolate, 186) by MCPBA in CH3OH. 117 Oxidation of 5-hydroxymethyl-5-methyl-2-thiono-2-ethoxy -1,3,2-dioxaphosphorinane (116) by SO2Cl2 in CDCl3_ 121 Reaction of BPS with SO2Cl2. 125 Alcoholysis of cyclic phosphates 132 Conclusion 144 Experimental 146 References 219 Appendices Appendix A: X-Ray data of rrans-5-acetoxymethyl-5-methyl -2-thiono-2-ethoxy-1,3,2-dioxaphosphorinane (119). 236 Appendix B: X-Ray data of trans-5-(3,5-Dinitro)benzoyloxymethyl-5. -methyl-2-thiono-r-2-ethoxy-1,3,2-dioxaphosphorinane ( 122). 240 Appendix C: X-Ray data of trans-5-chloromethyl-5-methy-2-thiono -r-2-ethoxy-1,3,2-dioxaphosphorinane ( 195). 245 Appendix D: X-Ray data of trans-5-hydroxymethyl-5-methyl -2-oxo-r-2-methoxy-1,3,2-dioxaphosphorinane (118). 248 (ix) Appendix E: X-Ray data of trans-5-hydroxymethyl-5-methyl -2-thiono-r-2-methox y-1,3 ,2-dioxaphosphorinane (203). 252 INTRODUCTION 1 The chemistry of phosphorothioates has been the subject of much attention, particularly with respect to defining the mechanism of action of insecticidally active I compounds. Of the approximately 106 organophosphorus pesticides in current use, phosphorothioates account for more than two thirds1 and in biological systems these are converted to metabolites which can be more toxic or less toxic than the parent compounds. These processes are termed "B ioacti vation" and "Detoxification", respectively. In many instances, these transformations are oxidatively induced, and these can be grouped into four broad classes of reactions, as illustrated below : (a) oxidative desulfuration of the thiophosphoryl group. s 0 a I 1 R- P-R1 R- P-R I I R~ R2 (b) conversion of a sulfide to a sulfoxide or sulfone. 0 0 t t ·1 1 1 R-S-R R-S-R R-S-R J. 0 (c) hydroxylation of an alkyl or aryl group. (d) N-oxidation of a phosphoramidate. 2 Of these transformations, oxidative desulfuration is particularly interesting because it normally results in a bioactivated compound. Oxidative desulfuration of the thiophosphoryl group has been shown to occur for a wide range of thiono-pesticides2 including phosphorothionates such as parathion (1), fenitrothion (2), phosphorothiolothionates such as dimethoate (3), and malathion (4) and phosphonothiolothionates such as fonofos (5). (2) (3) (1) (5) (4) Relative to the insecticidal activity of these compounds, the conversion is accepted as an activation process since the parent thiophosphoryl compounds are poor inhibitors of acetylcholinesterase whereas the phosphoryl derivatives are good inhibitors. To illustrate this point, LDso (rat, oral) data for selected phosphorothioates and their corresponding oxidative desulfuration products are given in Figure 1. These transformations can be brought about chemically, photochemically through exposure to sunlight, in animals by microsomal mixed function oxidases (mfo), or in plants by peroxidases. 3 3 (0] parathion (1) paraoxon 1.4 m50 3·3 s 0 D u (CH30)2P-S - CH- C02~Jis [0] (CH30)2P - S - CH-C02~H5 I I CJ½C02~H5 CH2C02~Hs malathion (4) malaoxon LDso 2600 308 [0] · fonofos (5). fonofos oxon LD50 14·7 2.8 Figure 1. Selected phosphorothionate pesticides, their oxidative desulfuration products and rat LDso values (oral, mg/kg).2 4 Oxidative desulfuration has received extensive chemical study, and a number of oxidants have been used to effect the transformation. These include peroxytrifluoroacetic acid,4 potassium permanganate,5 nitric acid,6 dimethyl sulfoxide7(or selenoxide8), ozone,9 dinitrogen tetroxide,10 hydrogen peroxide,11-13 and m-chloroperbenzoic acid (MCPBA) (6).11,14-34 However, if the results from the chemical studies are to be considered relevant to the biological system then the chemical model should mimic the biological oxidizing system as closely as possible. Specificially, it should show the same stereospecificity (retention of configuration) when chiral compounds are involved, and the newly introduced oxygen atom should come directly from the oxidant rather than from water.27 The oxidation by MCPBA has been considered to generally meet these requirements and the pattern of oxidation products was found to be similar to that of metabolic transformation. Therefore, the MCPBA-oxidation system has been widely used as a biomimic model for oxidation of not only phosphorothionates, 17,34 but also phosphorothiolates 22,23 and dithioates.14,20 More recently, in an attempt to improve the biomimetic model for relevance, the oxidations have been studied in aqueous solvents.
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