University of Montana ScholarWorks at University of Montana Graduate Student Theses, Dissertations, & Professional Papers Graduate School 1952 Reactions of olefin sulfides. I. Oxidation of trimethylene sulfide. II. Preparation of sulfenyl halides from profylene and trimethylene sulfide Charles Howard Burnside The University of Montana Follow this and additional works at: https://scholarworks.umt.edu/etd Let us know how access to this document benefits ou.y Recommended Citation Burnside, Charles Howard, "Reactions of olefin sulfides. I. Oxidation of trimethylene sulfide. II. Preparation of sulfenyl halides from profylene and trimethylene sulfide" (1952). Graduate Student Theses, Dissertations, & Professional Papers. 8225. https://scholarworks.umt.edu/etd/8225 This Thesis is brought to you for free and open access by the Graduate School at ScholarWorks at University of Montana. It has been accepted for inclusion in Graduate Student Theses, Dissertations, & Professional Papers by an authorized administrator of ScholarWorks at University of Montana. For more information, please contact [email protected]. REACTIONS OF OLEFIN SULFIDES I. OXIDATION OF TRimTHYLENE SULFIDE II, PREPARATION OF SÜLFENÏL HALIDES FROM PROPYLENE AND TRIMETHYLENE SULFIDE by CHARLES H. BURNSIDE 4P- B.A., Dakota Wesleyan University, 1947 Presented in partial fulfillment of the requirements for the degree of Master of Science MONTANA STATE UNIVERSITY 1952 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMI Number: EP39026 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMI* Oia»«wl*tion Publishing UMI EP39026 Published by ProQuest LLC (2013). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code uest ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. This thesis has been approved by the Board of Exam­ iners in partial fulfillment of the requirements for the degree of Master of Science. bka^man of the Ëoard of EJcaminers /Dean of the Graduate SchocôC Date ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS Page PART I INTRODUCTION................................. 2 Chapter I, DISCUSSION OF W O R K ........................ K II. EXPERIMNTAL .............................. 9 III. s u m u i R Y ........... 16 BIBLIOGRAPHY................................... 17 PART II INTRODUCTION ................................. 19 Chapter I. DISCUSSION OF W O R K ........................ 21 II. EXPERII-ENTAL.............................. 25 III. SUM«IARY.................................. 30 BIBLIOGRAPHY.................................. 31 ill Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. PART I OXIDATION OF TRII*ffiTHTLENE SULFIDE Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. INTRODUCTION The reactions of the four-membered heterocyclic sulfides have not been extensively studied* That these strained rings will open is to be expected, but by analogy with the four-membered carbocyclic compounds, these rings would be expected to be more stable than those of the three- membered heterocyclic sulfides. This has been shown to be the case. Both trimethylene sulfide and B, B-dimethyl tri- methylene sulfide will form salts with mercuric chloride. 1 *2 These cyclic sulfides will also form sulfones when treated with 30 per cent hydrogen peroxide or potassium permangan- ate. 1 * 2 Three-membered cyclic sulfide rings, due to strain, suffer cleavage of the carbon-sulfur bond on perox­ ide oxidation.^ Cleavage of the carbon-sulfur bond has been accom­ plished by treating the four-membered ring sulfides with various reagents. Methyl iodide cleaves the ring at the carbon-sulfur bond^»^»^ to give, in the case of trimethylene sulfide, 3-iodopropyl dimethyl sulfonium iodide.^ It has been postulated that this cleavage proceeds throu#i an un­ stable cyclic sulfonium intermediate.^ Trimethylene sul­ fide has been reported to polymerize in the presence of nitric acid and hydrochloric acids.The ring has also Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. -3- been opened by heating to 200 ® with ammonia, trimethylene sulfide yielding 3-aniinopropane-l-thiol*^Grishkevich 3 and Trokhimovski have also claimed ring cleavage when tri­ methylene sulfide was heated to 200 ® with water; however, the products of the reaction were not identified. Bost and Conn^ reported that trimethylene sulfide forms an addition compound with bromine which was, however, unstable, decom­ posing even at -15®. They failed to identify the decomposi­ tion products. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CHAPTER I DISCUSSION OF THE WORK The 3-membered sulfide ring in propylene sulfide is opened by such oxidizing agents as 30 per cent hydrogen per­ oxide, nitric acid, and the halogens, chlorine and bromine. With the halogens the nature of the cleavage products ob­ tained varied with the solvent u s e d . ^*7 aqueous chlorine l-chloro-propane-2-sulfonyl chloride was formed. Addition of chlorine or bromine to propylene sulfide in anhydrous solvents gave quantitative yields of bis-(l-methyl-2 -halo- ethyl) disulfides. With 30 per cent hydrogen peroxide, in addition to a primary cleavage and oxidation product, 2 - hydroxypropane-l-sulfonic acid, sulfuric acid was formed by the complete cleavage and oxidation of the sulfur atom. In this work the oxidation of trimethylene sulfide by these same oxidizing agents has been studied. As with propylene sulfide, the reaction of halogens produces dif­ ferent types of products in aqueoud and non-aqueous solu­ tion. When a calculated molar equivalent of chlorine was passed into a chloroform solution of trimethylene sulfide, bis-(3*chloropropyl)disulfide (I.) was produced in accord­ ance with the following equation: CHgCHgCHg + Clg — ^ClCHgCHgCHgSSGHjCHgCHjCl (I.) Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Sulfur analysis on (I) substantiates the structure shown. Treatment of (I) with excess piperidine, followed by an­ hydrous hydrogen chloride yieldéd a solid derivative, bis- (3-piperidlnopropyl)disulfide dihydrochloride, (II) then (CICH2 CH2 CH2 S2 -h 4 C5 H10N HCl-- CcH-iQWCHoCHjChjS ^ I-2KC1 -b 2 C H NH.HCl C5 H1QNCK2 CH2 CH2 S (II) Similarly trimethylene sulfide reacted readily with a molar equivalent of bromine to give an addition product which, however, was unstable to heating and could not be distilled without decomposition. The crude product was shown to be bis-(3-bromopropyl)disulfide by converting it to a solid derivative identical with (II) on treatment with piperidine followed by hydrogen chloride. Sulfur analysis on a sample of the crude bromine addition product, though not in close agreement with the calculated value, also sub­ stantiates the structure given. Three-chloropropane-l-sulfenyl chloride(III) has been prepared by the addition of a chloroform solution of trimethylene sulfide to liquid chlorine, reversing the order of addition described above. This reacts with tri­ methylene sulfide to give (I).^ Hence, the sulfenyl halide is probably an intermediate in the reaction in which the halogen is added to the sulfide. A probable mechanism for addition of halogen to trimethylene sulfide may be as fol­ lows: Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CHgCHgCHg'-S.lz-». ( çCH^CH^CHgj TC l “ > ClCH^CH^CH^SCl (III) Cl + — CHgCHgCH^ 4- ClCH^CHgCH^SCl —> { ) Cl >• ^ SCHgCHgCHgCl ClCHgCHgCHgSSCHgCHgCHgCl (I) When trimethylene sulfide and chlorine were reacted in 75 per cent acetic acid solution, the physical constants of the liquid product were found to be in close agreement to those of 3 -chloropropane-l-sulfonyl chloride which has been prepared by another method.^ Furthermore, the sulfonamide CHgCH^^Hg 4- 3CI2 4- 2 KgO ^acid"^ ClCHgCH^H^SOgCl 4-4 HCl derivative of (IV) was prepared and found to have a melting point identical with that of 3-chloropropane-l-‘Sulfonamide as reported by Kharasch et. al.^® In confirmation of some work reported by Bost and Conn^ it was found that treatment of trimethylene sulfide in petroleum ether with an acetic acid solution of the calculat­ ed amount of 30 per cent hydrogen peroxide followed by a short heating period gave trimethylene sulfone, C t ^ H g C ^ ^ . If, however, the petroleum ether was eliminated, and the sulfide was heated at reflux with excess 30 per cent hydro­ gen peroxide for about seven #ours, cleavage of the ring oc­ curred. As with results reported for propylene sulfide much of the sulfur was completely cleaved and oxidized to sulfuric acid. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. -7- A mixture of trimethylene sulfide and 30 per cent hydrogen peroxide, In 12