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The Chemistry of Non-Stabilized Sulfenes

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The Chemistry of Non-Stabilized Sulfenes Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1976 The heC mistry of Non-Stabilized Sulfenes. Huei-nan Lin Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Lin, Huei-nan, "The heC mistry of Non-Stabilized Sulfenes." (1976). LSU Historical Dissertations and Theses. 2928. https://digitalcommons.lsu.edu/gradschool_disstheses/2928 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. INFORMATION TO USERS This material was produced from a microfilm copy of the original document. 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Xerox University Microfilms 300 North Zaeb Road Ann Arbof, Michigan 48106 76-25,271 LIN, Huei-Nan, 1944- THE CHEMISTRY OF NON-STABILIZED SULFENES. The Louisiana State University and Agricultural and Mechanical College Ph.D., 1976 Chemistry, organic Xerox University Microfilms, Ann Arbor, Michigan 4B106 THE CHEMISTRY OF NON-STABILIZED SULFENES A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the Degree of Doctor of Philosophy in The Department o f Chemistry by Huei-Nan Lin B.S., Fu-Jen University, 1968 May, 19T6 For My Parents acknowledgment The author wishes to express his gratitude and appreciation to Dr. N. H. Fischer for his guidance, direction, and inspiration. Without Dr. Fischer's encouragement and patience, the accomplish­ ment of this work would have been impossible. Grateful acknowledgment is also recognized for the financial assistance from the Dr. Charles E. Coates Memorial Fund of the Louisiana State University Foundation for expenses incurred in the publication of this Dissertation. Special thanks are given to the author's cousin, Dr. Nai-Teng Yu, Associate Professor at the Georgia Institute of Technology, for his assistance and understanding during the author's study in the United States of America. The author is also grateful to his wife, Laura Hui-Shue, for her sacrifice of many weekends. iii TABLE OF CONTENTS PAGE ACKNOWLEDGMENT......................................................................................... i i i ABSTRACT ......................... v I . INTRODUCTION .................................................................................... 1 I I . RESULTS AND DISCUSSION ............................................................. 19 A. On the Mechanism of Sulfene Formation ............... 19 B. Attempted Generations of Non-stabilized Sulfenes 33 via Thermolysis of Bicyclic Sulfones ........................ C. Solvent E ffect and Neighboring Group 55 Participation in Sulfene Formation ........................... I I I . EXPERIMENTAL...................................................... 71 i. Reaction of Sulfonyl Chloride with Metal Hydrides ................................................................ 73 ii. Synthesis of Thietane-s,s-dioxides ........................ 77 iii. Synthesis of a-Thiopyran-1,1-dioxide and Thermolysis of Bicyclic Sulfones .......................... 79 iv. Reactions of D-Camphor-10-sulfonyl Chloride and Camphane-10-sulfonyl Chloride with Triethylamine ...................................................... 95 REFERENCES ................................................................................................. 106 APPENDIX A: Nmr S p e c tr a ............................................................... 113 APPENDIX B: I r S p e c tr a ...................................................................... 123 VITA.............................................................................................................. 133 iv ABSTRACT Sulfenes are comnonly generated from aliphatic sulfonyl chlorides with tertiary amines. The accepted E2 mechanism for the HCl-elimina- tion from the sulfonyl chloride was re-examined using bases other than tertiary amines. Bases of equal or higher strength than tertiary amines but 1cm nucleophilicity were chosen for the experiments. Aliphatic sulfonyl chlorides failed to react with sodium hydride, lithium hydride or the Corey base, bases which are generally con­ sidered to be stronger than tertiary amines. In a kinetic study, using phenylmethanesulfonyl chloride and triethylamine, a second order rate dependence for triethylamine was observed. Based on these experimental data, the E2 pathway for sulfene formation from aliphatic sulfonyl chlorides and tertiary amines is not likely. Instead, a mechanism involving initial attack of the tertiary amine at the sulfonyl group via a sulfone ammonium intermediate followed by proton abstraction (substitution-elimination pathway) is in agreement with the experimental results. A new method for the generation of non-stabilized sulfene by the thermolysis of allylic, bicyclic sulfones was attempted. Dimethyl 2,2-dioxido-2-thiabicyclo[2,2,2]octa-5,7*diene-5,6-dicar- boxylate and dimethyl 2 , 2-dioxido- 2-thiabicyclo[ 2 , 2 ,2 ]o c ta - 7-ene- 5 , 6 -dicarboxylate were thermolyzed with and without sulfene trapping agents. The thermolysis reactions proceeded via a novel SOg- extrusion-rearrangement reaction under formation of cycloheptatriene derivatives. Trapping experiments involving electron rich alkenes (enamines) did not lead to detectable amounts of sulfene cyclo- addition products. v Attempted cycloaddition reactions between in situ generated sulfene (methanesulfonyl chloride/triethylamine) and an electron deficient diene (thiopyrane- 1, 1-dioxide) were without success. The chemistry of D-camphor-10-sulfonyl chloride with tr i­ ethylamine, a reaction known for many decades, was explored in greater detail. (Z)- and (E)-D-camphor-lO-chlorosulfoxide were successfully separated and obtained in pure form. In contrast to the reaction of phenylmethanesulfonyl chloride and triethylamine, the reaction of D-camphor- 10-sulfonyl chloride with triethylamine did not show any solvent dependence. The lack of solvent dependence is attributed to the involvement of the camphor-carbonyl oxygen which stabilizes the positive carbon center of the sulfene inter­ mediate by neighboring group participation. Experimental evidence for the necessity of the carbonyl group in the formation of the D-camphor-10-chlorosulfoxides was provided by the reaction of camphane-10-sulfonyl chloride with triethylamine. The latter reaction failed to give camphan«-10-chlorosulfoxides. Instead, the aldehyde 7,T-dimethyl-l-formylbicyclo[2,2,l']heptane was formed in low y ie ld . vi I. INTRODUCTION Several reviews related to the generation and chemistry of sul­ fenes have appeared in recent years . 1 ,2 ,a ’4 Therefore, this intro­ duction is not intended to represent a comprehensive review on sul­ fenes but to briefly summarize methods of generation and the most typical reactions of sulfenes. Formally, sulfenes are the S,S'-dioxides of thioaldehydes (_1, R ■ a lk y l, a ry l R' 3 H) or thioketones (l.> R * R' » alkyl, aryl). R 0 R 0 1 They can also be classified as the inner anhydride of sulfonic acids, just as ketenes represent the inner anhydrides of carboxylic acids. Furthermore, they can be looked at as derivatives of sulfur trioxide, in which one oxygen atom is replaced by an alkylidene group .2 In sulfenes, all the electrons of the sulfur atoms are involved in bonding. From the reactions of sulfene with various reagents, it can be concluded that several resonance forms (la-W) may be formulated for this molecule.
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