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Free Radical Reactions of Organomercurials De-Liang Guo Iowa State University

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Free Radical Reactions of Organomercurials De-Liang Guo Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1989 Free radical reactions of organomercurials De-Liang Guo Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Guo, De-Liang, "Free radical reactions of organomercurials " (1989). Retrospective Theses and Dissertations. 9126. https://lib.dr.iastate.edu/rtd/9126 This Dissertation 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 Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS The most advanced technology has been used to photo­ graph and reproduce this manuscript from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. 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University Microfilms International A Bell & Howell Information Company 300 North Zeeb Road, Ann Arbor, Ml 48106-1346 USA 313/761-4700 800/521-0600 Order Number 9014901 Free radical reactions of organomercurials Guo, De-Liang, Ph.D. Iowa State University, 1989 UMI SOON.ZeebRd. Ann Aibor, MI 48106 Free radical reactions of organomercurials by De-Liang Guo A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Department: Chemistry Major: Organic Chemistry Approved: lumbers of the Committee: Signature was redacted for privacy. In (Sjharge of Major Work Signature was redacted for privacy. Signature was redacted for privacy. For the MajorD^artmem Signature was redacted for privacy. For the Graduate College lowa State University Ames, Iowa 1989 Copyright (c) De-Liang Guo, 1989. All rights reserved. ii TABLE OF CONTENTS GENERAL INTRODUCTION 1 PART I. CHEMICALLY INDUCED DYNAMIC NUCLEAR PO­ LARIZATION (CIDNP) OBSERVED DURING OXIDATION OF ORGANOMERCURIALS 2 CHAPTER 1. INTRODUCTION 3 CHAPTER 2. THEORETICAL CALCULATION OF THE CIDNP EFFECT BY THE CKO METHOD (CLOSS, KAPTEIN, OoST- ERHOFF) 6 The Radical-pair Model 6 Concept of the radical pair 6 The generation of the disappearance of the radical pair 6 First-order Spectra (CIDNP Intensities) 7 Kaptein's Rules 8 CHAPTER 3. RESULTS AND DISCUSSION 10 The System, i-BuHgCl/S20g~/NaI 10 The System, RHgX/S20g~ 16 iii Peroxydisulfate ions and sulfate radical ions 16 (CH3)3CHgCl/(NH4)2S208 18 (CH3)2CHHgX/(NH4)2S208 X=Cl,Br,I 22 CH3CH2HgX/S20|- X=C1, I 24 M-C^HgHgCl/ (NH4)2S208 26 n-CgHiiHgCl/ (NH4)2S208 28 (CH3)3CCH2CH2HgCl/(NH4)2S208 28 2-Methoxycyclohexylmercury chloride/ S2O8 31 RHgCl/S20|~ (R = C-C5H11, c-CgHig and c-CjHn) 37 The System, R2Hg/S20g~ 37 (f-Bu)2Hg/S20|- 37 Et2Hg/(NH4)2S20|- 40 PhSEgC(CH3)3/S20^- 42 The System, RHgCl/S20g~/RI 45 MeHgCl/S20|~/RI 45 Cl3CHgCl/S20|-/RI 47 c-C3H5HgBr/S20^~/RI 50 ClHgCH2CHO/S20|~/CH3CH2l 54 The System, R2Hg/S208~/RI 57 Ph2Hg/S202-/RI 57 ((Et0)2P0)2Hg/S20|-/EtI 61 (PhC0CH2)2Hg/S20|-/(CH3)2CHI 63 The System, RHgN03/(NH4)2S20g/AgN03 64 iv (CH3)2CHHgN03/ (NH4)2S208/AgN03 65 CH3CH2HgN03/(NH4)2S208/AgN03 68 (C:H3)3CHgSPh/ (NH4)2S208/AgN03 71 ((CH3)3C)2Hg/Hg(N03)2 74 The System, Ph3Sb/(NH4)2S208/(CH3)2CHI 77 The System, RC00H/S20g" 79 (CH3)3CC00H / S20|~ 80 (CH3)2CHC00H/S20|~ 84 (CH3)2CH00H/S20|"/AgN03 88 The System, (CH3)3CCH0/S20|~ 93 The System, (CH3)3CCH0/S20^~/AgN03 96 CHAPTER 4. CONCLUSION 98 CHAPTER 5. EXPERIMENTAL 100 PART IL PHOTOSTIMULATED FREE-RADICAL CHAIN RE­ ACTIONS OF ALKYLMERCURIALS WITH HETEROARO- MATIC COMPOUNDS 101 CHAPTER 1. INTRODUCTION 102 CHAPTER 2. RESULTS AND DISCUSSION 106 Reactions of RHgX with Pyridine 106 Evidence for a Free Radical Chain Process 106 Determination of the Kinetic Chain Length of the Reaction between t- BuHgCl and 7-picoline 109 V Reactions of RHgX with Substituted Pyridines Ill Reactions of ier<-butyl radical with 4-substituted pyridines Ill Reactions of (er^-butyl radical with 3-substituted pyridines 112 Reactions of ier^-butyl radical with 2-substituted pyridines 112 Reactions of ferf-BuHgCl with phenylpyridines 113 Reactions of Cyclopentylmercury Chloride with Pyridine and Anthracene . 113 Reactions of RHgX with Protonated or Unprotonated Heteroaromatic Com­ pounds 114 Regioselectivity and Reactivity 116 Reactions of Alkylmercury Chlorides with (s)-( —)-Nicotine 125 Solvomercuration-pyridination 127 Reaction of 5-ea:o-Methoxy-3-eio-nortricyclylmercury Chloride with Pyri­ dine or Quinoline 133 Reaction of RHgX with N,N,N',N'-tetramethyl-p-phenylene-diamine .... 137 CHAPTER 3. CONCLUSION 145 CHAPTER 4. EXPERIMENTAL 146 General Considerations 146 ^H NMR of Mono-alkylated Pyridines 147 Reaction of Cyclohexylmercury Chloride with Pyridine 148 Reaction of eio-2-Norbornylmercury Chloride with Pyridine 152 Reaction of u-Butylmercury Chloride with Pyridine 153 Reaction of Cyclopentylmethylmercury Chloride with Pyridine 153 Reaction of ^-Acetaminocyclohexylmercury Chloride with Pyridine .... 154 vi Oxymercuration-pyriclination of Cydohexene 155 Methoxymercuration-pyridination of Cydohexene 156 Methoxymercuration-pyridination of cis,cis-l,5-Cycloctadiene 156 Reaction of Benzylmercury Chloride with N,N,N',N'-Tetramethyl-p-phenylene- di amine 160 General Procedure for the Photostimulated Reactions of RHgCl with Pyri­ dine or Heteroaromatic Compounds 160 Reaction of 5- ezo-Methoxy-3- ezo-nortricyclylmercury Chloride with Pyridine 161 Reaction of 5-ea:o-Methoxy-3-eso-nortricyclylmercury Chloride with Lepidine 167 PART III. FREE-RADICAL OXIDATION-REDUCTION REAC­ TIONS OF RHgX WITH ORGANIC UNSATURATED COM­ POUNDS 170 CHAPTER 1. INTRODUCTION 171 CHAPTER 2. RESULTS AND DISCUSSION 174 Evidence of RHgX"^* from RHgX Mass Spectra 174 Evidence of R# 176 Calculations of Electron Transfer Rates from i-BuHgCI to SO^* by the Marcus Equations 178 Reactions of RHgX with a, /3-Unsaturated Carbonyl Compounds in the Presence of S20g~/I"~ 181 AHiylation of Uracil 184 Alkylation of Quinone 187 vii Alkylation of Maleic Anhydride 192 Reaction of i-BuHgCl and Pyridine or PyHgCl2 with Oxidizing Reagents . 195 Reaction of f-BuHgCl and PyHI with Oxidizing Reagents 198 Phenylation of Organic Compounds with PhgHg 200 Evidence for [RHgX~*] 203 Reactivity of the 5-Hexenyl Radical toward the Anion of 2-Nitropropane and Borohydride Anion 205 CHAPTER 3. CONCLUSION 212 CHAPTER 4. EXPERIMENTAL 213 General Considerations 213 Reaction of f-BuHgCl with Uracil in Presence of S20g~/Nal 214 Reaction of f-BuHgCl with Acrylamide in Presence of SgOg^/Nal 215 Reaction of i-BuHgCl with NPQN in Presence of S20g~ / Nal / Dabco . 215 Reaction of z-PrHgNOg with 1,4-Naphthoquinone in Presence of S20g~/Ag~'"216 Reaction of i-PrHgNOg with 2-Methyl-l,4-naphthoquinone in Presence of S2O0-/Ag+ 216 General Procedure for the Chemical Oxidation of RHgX with tt Compounds in Presence of S20|~ / Nal or AgNOg 217 GENERAL SUMMARY 224 BIBLIOGRAPHY 226 ACKNOWLEDGEMENTS 233 viii LIST OF TABLES Table 3.1: Thermal decomposition of initiators 17 Table 3.2: NMR 6 value obtained during the reaction of (CHg)gCGOOH and S20^~/Ag+ 93 Table 2.1: Photostimulated reactions of RHgCl with pyridine 107 Table 2.2; Reactions of RHgCl with protonated pyridine, 4-picoline and lepidine 115 Table 2.3: Reactions of RHgCl with benzothiazole, isoquinoline and lep­ idine (substrates) 116 Table 2.4: The solvent effect on the regioselectivity of the 2- and 4- po­ sition in pyridine 117 Table 2.5: The acidity effect on the regioselectivity of the 2- and 4- posi­ tion in pyridine 118 Table 2.6: 'Adjusted' unperturbed molecular orbital energies (eV) used in the interaction energy calculation 122 Table 2.7: 6-Alkylnicotines prepared from the reaction of RHgCl with (a)-( —) nicotine with sunlamp irradiation 126 ix Table 2.8: Alkylpyridines formed by the reaction of an alkene with Hg(0Ac)2 followed by reaction with C5H5N with sunlamp irradiation . 129 Table 2.9: Alkylpyridines formed by the reaction of an alkene with Hg(TFA)2 and MeOH followed by reaction with C5H5N with sunlamp ir­ radiation 131 Table 2.10: Photostimulated reactions of RHgCl with TMPDA 143 Table 4.1: GCMS data for the products of the photostimulated reaction between RHgX and pyridine 149 Table 4.2: GCMS for alkylpyridines formed by the reaction from alkene with Hg(TFA)2 / MeOH followed by the photostimulated re­ action with pyridine 158 Table 4.3: NMR data for the products of the photostimulated reaction between i-BuHgCl and substituted pyridines 162 Table 4.4: GCMS and HRMS data for the products of the photostimu­ lated reaction between t-BuHgCl and substituted pyridines .
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