DOCSLIB.ORG

Jones Isomers”

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text

Load more

BIOSYNTHETIC STUDIES OF OTTELIONE A AND THE STRUCTURAL RE-ANALYSIS OF THE “JONES ISOMERS” THE STRUCTURAL REASSIGNMENT OF PHOMOPSICHALASIN TO THAT OF DIAPORTHICHALASIN A DISSERTATION SUBMITTED TO THE FACULTY OF THE GRADUATE SCHOOL OF THE UNIVERSITY OF MINNESOTA By Susan G. Brown IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY Thomas R. Hoye, Adviser February 2013 © Susan G. Brown 2013 Portions © J. Nat. Prod. 2012 and used with permission i ACKNOWLEDGEMENTS Firstly I would like to thank my adviser professor Thomas Hoye for his patience, guidance and mentorship throughout my time spent in his group. His keen ability to hone in on the details of the problem at hand has made me into the chemist that I am today. To professors Andrew Harned, Wayland Noland and Robert Fecik, thank you for serving as members on my committee as well as for the helpful conversations along the way. I would also like to thank my undergraduate adviser, professor Rebecca Hoye. Becky, your mentorship and willingness to always serve as a listening ear was truly indispensable both throughout my time at Macalester and the University of Minnesota. To my friends from the “consulate”, thank you for making Minnesota my home away from home for the past several years. Finally to my mother and father, Dothlyn and Albert, your unwavering love and support has enabled the completion of this thesis. Thank you for being devoted parents. ii DEDICATION To my mother and father, Dothlyn and Albert Brown. iii ABSTRACT Part I Ottelione A, isolated from the fresh water plant Ottelia alismoides, is a cytotoxic agent at nanomolar levels against 60 human cancer cell lines. Among other compounds isolated were a group of novel 1,7-diarylheptanoids. We propose that one of these diarylheptanoids shares a biogenetic linkage with ottelione A. Namely, we hypothesize that a spontaneous (i.e., non-enzyme catalyzed) Cope rearrangement, almost entirely unprecedented in nature, is central to the biosynthesis of ottelione A. The successful synthesis of the hypothesized biologically relevant diarylheptanoid has now enabled us to probe its possible biogenetic linkage to ottelione A. During the course of our studies we have also performed the structure reanalysis of two related hydrienone compounds that share the exact same core as ottelione A. Part II Phomopsichalasin, a cytochalasin-like secondary metabolite, was isolated from an endophytic fungus Phomopsis sp. in 1995. Diporthichalasin, from the endophytic fungus Diaporthe sp. Bkk3, was isolated several years later in 2007. Both were assigned different structures and their spectroscopic characterization reported in two different solvents. By way of detailed NMR analysis and pertinent computational models we have demonstrated that the structure originally proposed for Phomopsichalasin was incorrect and is in fact that of the more recently isolated compound Diaporthichalasin. TABLE OF CONTENTS Acknowledgements i Dedication ii Abstract iii Table of Contents iv-vi List of Tables vii-viii List of Figures ix-xii List of Abbreviations xiii-xv PART I : BIOSYNTHETIC STUDIES OF OTTELIONE A AND THE STRUCTURAL RE-ANALYSIS OF THE “JONES ISOMERS” Chapter I. A potential role for diarylheptanoids in the biosynthesis of ottelione A I-A. Introduction and Background I-A1. Isolation, structural characterization and biological activity of the otteliones 2-5 I-A-2. Biosynthetic hypothesis 5-9 I-A-3. Prior accounts of the Cope rearrangement in nature 9-13 I-A-4. Synthetic strategies toward otteliones A and B 14-15 I-B. Diarylheptanoids in nature I-B-1. Introduction 16-18 I-B-2. Synthesis of 177 and 178 19-24 I-C. Future Studies 25 I-D. Concluding remarks 26 Chapter II. The Cope rearrangement within the strained [m]-cyclophane 204-prox II-A. Background II-A-1. Introduction 27-29 II-A-2. First generation synthesis of 204-prox 29-32 II-B. Efforts toward the improved synthesis of 204-prox II-B-1. Synthesis of 209 – A chromatographic solution 33-34 II-B-2. A thiol-ene click strategy 35-39 II-B-3. Double β-alkyl Suzuki reaction 39-45 II-B-4. Intramolecular displacement of allyl halides 45-48 II-C. Progress toward the synthesis of [9]-paracyclophane 298 II-C-1. Synthesis of 2107 and attempted cyclization 49-50 II-D. Concluding Remarks 51 Chapter III. Flash vacuum pyrolysis experiments and the structural reassignment of the Jones Isomers III-A. Flash vacuum pyrolysis II-A-1. Introduction 52-54 II-A-2. Relevant FVP experiments 54-55 II-A-3. Synthesis and FVP of 321 55-71 III-B. Evidence in support of the structural reassignment of 322-endo to 323-endo and 323-endo to 323-exo. III-B-1. Computational support 72-73 III-B-2. Addressing the constitution of Isomer I: 322-endo vs. 323-endo 73-75 III-B-3. Relative configuration of Isomer II: 323-endo vs. 323-exo 76-79 III-B-4. Crucial NOE experiments 79-80 III-C. Concluding remarks 81 PART II : REASSIGNMENT OF THE RELATIVE CONFIGURATION OF PHOMOPSICHALASIN Chapter IV. The hexa-epimers phomopsichalasin and diaporthichalasin IV-A. Background IV-A-1. Introduction 83-85 IV-A-2. Biosynthetic hypothesis 85-87 IV-A-2. Spectroscopic ambiguity surrounding the structure assigned to phomopsichalasin 88-89 IV-B. Previous synthetic efforts IV-B-1. Progress towards the synthesis of ‘phomopsichalasin’ – Structure determination via synthesis 90-91 IV-C. A case for the structural reassignment of phomopsichalsin IV-C-1. Computational support 92 IV-C-2. Spectroscopic support 93-99 IV-C-3. Miscellaneous observations – dehydration and oxidative degradation of 402 100 IV-D. Concluding remarks 101 Experimental 102-183 Bibliography 184-191 vii LIST OF TABLES Table I-1. Half-life, temperature, and energy of activation (experimental and computational) of Cope rearrangement within 1,5-hexadiene (137), cis-divinylcyclopropane (130), and bullvalene (138); the known types of Cope rearrangement relevant to natural product biosynthesis [139 (pre-ectocarpene) to ectocarpene and 140 (vis-à-vis welwitindolinones and dragmacidin E)]. aDFT B3LYP/6-31G. bSCF-MO (MIND0/2). cOur estimate based on reported NMR data. dCalculated using this estimated t1/2 and the Arrhenius factor from the parent divinylcyclopropane 130…………………….…………..…………..11 Table I-2. NMR spectral data for 4-((1E,4E)-7-(4 hydroxyphenyl)hepta-1,4-dien-1-yl)-2-methoxyphenol (177) in CDCl3……………………………..…………………….….23 Table I-3. NMR spectral data for 4-((1E,4E)-7-(4 hydroxyphenyl)hepta-1,4-dien-1-yl)benzene-1,2-diol (178) in CDCl3……………………..………………………….....….23 Table II-1. Conditions screened in the quest of conducting the double β-alkyl Suzuki………………………….……….........….41 Table III-1. NMR spectral data for (1R,3aR,7aS)-7-methylene- 1-vinyl-3,3a,7,7a-tetrahydro-1H-inden-4(2H)-one (323-endo) in CDCl3......…………………………………..….……..63 Table III-2. NMR spectral data for (1R,3aR,7aS)-7-methylene- 1-vinyl-3,3a,7,7a-tetrahydro-1H-inden-4(2H)-one (323-endo) in methanol-d4……………………………...……….…..64 Table III-3. NMR spectral data for (1R,3aR,7aS)-7-methylene- 1-vinyl-3,3a,7,7a-tetrahydro-1H-inden-4(2H)-one (323-endo) in CDCl3, methanol-d4, and acetone-d6…...……….…....65 Table III-4. NMR spectral data for (1S,3aR,7aS)-7-methylene- 1-vinyl-3,3a,7,7a-tetrahydro-1H-inden-4(2H)-one (323-exo) in CDCl3......…………………………………..….…..…..66 viii Table III-5. NMR spectral data for (1S,3aR,7aS)-7-methylene- 1-vinyl-3,3a,7,7a-tetrahydro-1H-inden-4(2H)-one (323-exo) in methanol-d4.……………………………...…….….…..67 Table III-6. NMR spectral data for (1S,3aR,7aS)-7-methylene- 1-vinyl-3,3a,7,7a-tetrahydro-1H-inden-4(2H)-one (323-exo) in CDCl3, methanol-d4, and acetone-d6.…...……….….....68 Table III-7. NMR spectral data for (5aR,8aS)-1,2a1,4,5a,6,8a- hexahydroacenaphthylen-5(2H)-one in CDCl3.…...……….……......69 Table III-8. NMR spectral data for (5aR,8aS)-1,2a1,4,5a,6,8a- hexahydroacenaphthylen-5(2H)-one in methanol-d4.…...………......70 Table III-9. NMR spectral data for (5aR,8aS)-1,2a1,4,5a,6,8a- hexahydroacenaphthylen-5(2H)-one in CDCl3, methanol-d4, and acetone-d6.…........................................…….…......71 Table IV-1. NMR spectral data for diaporthichalasin (402) in d4-methanol (UMN)….…...………………………………....…....94 Table IV-2. NMR spectral data for diaporthichalasin (402) in d6-DMSO….…….…...…………………………………....….......95 Table IV-2. NMR spectral data for diaporthichalasin (402) in CDCl3….…….…...…………………………………....….............96 ix LIST OF FIGURES Figure I-1. Panel A. Structures of otteliones A and B; Panel B: p-cresol Tautomer RPR115781………………......…..……...………3 Figure I-2. Panel A. Hoye’s first proposal of the structure for ottelione A (101) Panel B. Hoye’s first proposal of the structure for ottelione B (102)……………….……………….....…...3 Figure I-3. Structure activity relationship of ottelione A…...…...………………4 Figure I-4. Collection of diarylheptanoids isolated by Hoye and coworkers…...……...………………………………………………..6 Figure I-5. Hoye and coworkers wonder if there was a biosynthetic linkage between compounds, 107 and 101…………………...……...6 Figure I-6. A small representative sample of natural products derived from the Diels-Alder cycloaddition………..………...……...9 Figure I-7. Conditions used for the epimerization of ottelione A (101) to ottelione B (102)…………..………………….…………..……...14 Figure I-8. The five types of 1,7-diarylheptanoids……...……..……..………...16 Figure I-9. Generic structures of families of diarylheptanoid (I), biarylheptanoid (II), anddiaryletherheptanoid (III) natural products………………..…………..…………..…………...18 Figure II-1. Panel A: Biosynthetic formation of ottelione A (101) from [m]-cyclophane 115. Panel B: Truncated analogous of 101 (202-exo) and 115 (201) lacking the benzyl substituent……………..…………..……..…..……...……...27 Figure II-2. Cope rearrangement with the strained compound 201 to 202-exo. 201 can be accessed from the K.E.T. from 203 that is made from the MOM-protected phenol 204-prox.……………..…………..……..…..……....……...28 Figure II-3.
Recommended publications
  • The Destructive Distillation of Pine Sawdust

    The Destructive Distillation of Pine Sawdust

    Scholars' Mine Bachelors Theses Student Theses and Dissertations 1903 The destructive distillation of pine sawdust Frederick Hauenstein Herbert Arno Roesler Follow this and additional works at: https://scholarsmine.mst.edu/bachelors_theses Part of the Mining Engineering Commons Department: Mining Engineering Recommended Citation Hauenstein, Frederick and Roesler, Herbert Arno, "The destructive distillation of pine sawdust" (1903). Bachelors Theses. 238. https://scholarsmine.mst.edu/bachelors_theses/238 This Thesis - Open Access is brought to you for free and open access by Scholars' Mine. It has been accepted for inclusion in Bachelors Theses by an authorized administrator of Scholars' Mine. This work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the permission of the copyright holder. For more information, please contact [email protected]. FOR THE - ttl ~d IN SUBJECT, ••The Destructive Distillation of P ine Sawdust:• F . HAUENSTEIN AND H . A. ROESLER. CLASS OF 1903. DISTILLATION In pine of the South, the operation of m.ills to immense quanti waste , such and sawdust.. The sawdust especially, is no practical in vast am,ounte; very difficult to the camp .. s :ls to util the be of commercial .. folloWing extraction turpentine .. of the acid th soda and treat- products .. t .. the t.he turpentine to in cells between , or by tissues to alcohol, a soap which a commercial t this would us too the rd:- hydrochloric was through supposition being that it d form & pinene hydro- which produced~ But instead the hydrochl , a dark unl<:nown compound was The fourth experiment, however, brought out a number of possibilities, a few of Which have been worked up.
  • Hardwood-Distillation Industry

    Hardwood-Distillation Industry

    HARDWOOD-DISTILLATION INDUSTRY No. 738 Revised February 1956 41. /0111111 110 111111111111111111 t I 1, UNITED STATES DEPARTMENT OF AGRICULTURE FOREST PRODUCTS LABORATORY FOREST SERVICE MADISON 5, WISCONSIN. In Cooperation with the University of Wisconsin 1 HARDWOOD-DISTILLATION INDUSTRY— By EDWARD BEGLINGER, Chemical Engineer 2 Forest Products Laboratory, — Forest Service U. S. Department of Agriculture The major portion of wood distillation products in the United States is obtained from forest and mill residues, chiefly beech, birch, maple, oak, and ash. Marketing of the natural byproducts recovered has been concerned traditionally with outlets for acetic acid, methanol, and charcoal. Large and lower cost production of acetic acid and methanol from other sources has severely curtailed markets formerly available to the distillation in- dustry, and has in turn created operational conditions generally unfavor- able to many of the smaller and more marginal plants. Increased demand for charcoal, which is recovered in the largest amount as a plant product, now provides a compensating factor for more favorable plant operation. The present hardwood-distillation industry includes six byproduct-recovery plants. With the exception of one smaller plant manufacturing primarily a specialty product, all have modern facilities for direct byproduct re- covery. Changing economic conditions during the past 25 years, including such factors as progressively increasing raw material, equipment, and labor costs, and lack of adequate markets for methanol and acetic acid, have caused the number of plants to be reduced from about 50 in the mid- thirties to the 6 now operating. In addition to this group, a few oven plants formerly practicing full recovery have retained the carbonizing equipment and produce only charcoal.
  • Xarox University Microfilms

    Xarox University Microfilms

    INFORMATION TO USERS Thil material was produced from a microfilm copy of the original documant. While the moat advanced technological meant to photograph and reproduce this documant have been used, the quality is heavily dependant upon the quality of the original submitted. The following explanation o f techniques is provided to help you understand markings or patterns which m ay appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Misting Page(s)". If it was possible to obtain the misting page(s) or section, th a y era spliced into the film along with adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pagae to insure you complete continuity. 2. Whan an image on th e film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus causa a blurred image. You will find a good image of the pnga in the adjacent frame. 3. Whan a map, drawing or chart, etc., was part of the material being photographed the photographer followed a definite method in "sectioning" the material. It ie customary to begin photoing at the upper left hand comer of a large sheet and to continue photoing from left to right in equal sections with a small overlap. If necessary, sectioning is continued again — beginning below the first row end continuing on until complete. 4. The majority of users indicate that the textual content is of greatest value, however, a somewhat higher quality reproduction could be made from "photographs" if essential to the understanding of the dissertation.
  • ( 463 ) XXXII. on the Products of the Destructive Distillation of Animal

    ( 463 ) XXXII. on the Products of the Destructive Distillation of Animal

    ( 463 ) XXXII. On the Products of the Destructive Distillation of Animal Substances. Part I. By THOMAS ANDERSON, Esq., M.D. (Read 3d April 1848.) In April 1846, I communicated to the Royal Society a paper on a new organic base, to which I gave the name of Picoline, and which occurs in coal-tar, asso- ciated with the Pyrrol, Kyanol, and Leukol of RUNGE. In that paper I pointed out that the properties of picoline resembled, in many respects, those of a base which UNVERDORBEN had previously extracted from DIPPEL'S animal oil, and described under the name of Odorine; and more especially mentioned their solubility in water, and property of forming crystallisable salts with chloride of gold, as cha- racters in which these substances approximated very closely to one another. And further, I detailed a few experiments on the odorine of UNVEBDORBEN extracted from DIPPEL'S oil, with the view of ascertaining whether or not they were ac- tually identical, but on too small a scale to admit of a definite solution of the question. These observations, coupled with the doubts which had been expressed by some chemists, and more especially by REICHENBACH, as to the existence of the bases described by UNVERDORBEN, induced me to take up the whole subject of the pro- ducts of the destructive distillation of animal substances, which has not yet been investigated in a manner suited to the requirements of modern chemistry. In fact, UNVERDORBEN is the only person who has examined them at all, and his experiments, contained in the 8th and 11th volumes of POGGENDORF'S Annalen, constitute the whole amount of our knowledge on the subject; and his observa- tions, though valuable, and containing perhaps as much as could easily be deter- mined at the time he wrote, are crude and imperfect, when we come to compare them with those which the present state of the science demands.
  • Origin and Resources of World Oil Shale Deposits - John R

    Origin and Resources of World Oil Shale Deposits - John R

    COAL, OIL SHALE, NATURAL BITUMEN, HEAVY OIL AND PEAT – Vol. II - Origin and Resources of World Oil Shale Deposits - John R. Dyni ORIGIN AND RESOURCES OF WORLD OIL SHALE DEPOSITS John R. Dyni US Geological Survey, Denver, USA Keywords: Algae, Alum Shale, Australia, bacteria, bitumen, bituminite, Botryococcus, Brazil, Canada, cannel coal, China, depositional environments, destructive distillation, Devonian oil shale, Estonia, Fischer assay, Fushun deposit, Green River Formation, hydroretorting, Iratí Formation, Israel, Jordan, kukersite, lamosite, Maoming deposit, marinite, metals, mineralogy, oil shale, origin of oil shale, types of oil shale, organic matter, retort, Russia, solid hydrocarbons, sulfate reduction, Sweden, tasmanite, Tasmanites, thermal maturity, torbanite, uranium, world resources. Contents 1. Introduction 2. Definition of Oil Shale 3. Origin of Organic Matter 4. Oil Shale Types 5. Thermal Maturity 6. Recoverable Resources 7. Determining the Grade of Oil Shale 8. Resource Evaluation 9. Descriptions of Selected Deposits 9.1 Australia 9.2 Brazil 9.2.1 Paraiba Valley 9.2.2 Irati Formation 9.3 Canada 9.4 China 9.4.1 Fushun 9.4.2 Maoming 9.5 Estonia 9.6 Israel 9.7 Jordan 9.8 Russia 9.9 SwedenUNESCO – EOLSS 9.10 United States 9.10.1 Green RiverSAMPLE Formation CHAPTERS 9.10.2 Eastern Devonian Oil Shale 10. World Resources 11. Future of Oil Shale Acknowledgments Glossary Bibliography Biographical Sketch Summary ©Encyclopedia of Life Support Systems (EOLSS) COAL, OIL SHALE, NATURAL BITUMEN, HEAVY OIL AND PEAT – Vol. II - Origin and Resources of World Oil Shale Deposits - John R. Dyni Oil shale is a fine-grained organic-rich sedimentary rock that can produce substantial amounts of oil and combustible gas upon destructive distillation.
  • 37Th Rocky Mountain Conference on Analytical Chemistry

    37Th Rocky Mountain Conference on Analytical Chemistry

    Rocky Mountain Conference on Magnetic Resonance Volume 37 37th Rocky Mountain Conference on Article 1 Analytical Chemistry July 1995 37th Rocky Mountain Conference on Analytical Chemistry Follow this and additional works at: https://digitalcommons.du.edu/rockychem Part of the Chemistry Commons, Materials Science and Engineering Commons, and the Physics Commons Recommended Citation (1995) "37th Rocky Mountain Conference on Analytical Chemistry," Rocky Mountain Conference on Magnetic Resonance: Vol. 37 , Article 1. Available at: https://digitalcommons.du.edu/rockychem/vol37/iss1/1 This work is licensed under a Creative Commons Attribution 4.0 License. This Article is brought to you for free and open access by Digital Commons @ DU. It has been accepted for inclusion in Rocky Mountain Conference on Magnetic Resonance by an authorized editor of Digital Commons @ DU. For more information, please contact [email protected],dig- [email protected]. et al.: 37th RMCAC Final Program and Abstracts 37TH ROCKY MOUNTAIN CONFERENCE ON ANALYTICAL CHEMISTRY FINAL PROGRAM AND ABSTRACTS JULY 23-27, 1995 HYATT REGENCY DENVER 1750 WELTON STREET DENVER, COLORADO SPONSORED BY: ROCKY MOUNTAIN SECTION SOCIETY FOR APPLIED SPECTROSCOPY & COLORADO SECTION AMERICAN CHEMICAL SOCIETY Published by Digital Commons @ DU, 1995 1 Rocky Mountain Conference on Magnetic Resonance, Vol. 37 [1995], Art. 1 TABLE OF CONTENTS Conference Organizers 2 Symposia Organizers 3 Registration and Event Information 5 Exhibitor List 8 Hotel and Visitor Information 9 Employment Clearing House and Professional Memberships 9 Short Courses 10 Vendor Workshops 12 Symposia Schedule: Atomic Spectroscopy 17 Chromatography 18 Compost (Biogeochemistry of) 19 Electrochemistry 20 Environmental Chemistry 22 EPR 25 FTIR/NIR/RAMAN Spectroscopy 37 General Posters 37 ICP-MS 39 Laboratory Safety 41 Luminescence 42 Mass Spectrometry 44 NMR 47 Pharmaceutical Analysis 59 Quality Assurance 60 Downtown Denver Street Map Inside back cover Abstracts start after page 61.
  • Modern Technology of Dry Distillation of Wood

    Modern Technology of Dry Distillation of Wood

    Modern technology of dry distillation of wood Michał LEWANDOWSKI, Eugeniusz MILCHERT – Institute of Chemical Organic Technology, Faculty of Chemical Technology and Engineering, West Pomeranian University of Technology, Szczecin Please cite as: CHEMIK 2011, 65, 12, 1301-1306 Nowadays the process of dry (destructive) distillation of wood is Wood gas from dry distillation contains (%wt.): CO2 40-55, carried out in a periodical (batch) or continuous manner. In the former CO 26-35, CH4 3-10, C2H4 2, H2 1-4. It is often used for steam case steel (mobile) retort furnaces are used, while in the latter case, generation for captive use at the distillation plant or in nearby facilities, science • technique retorts included in automated plants. In both cases temperature during or directly as fuel for heating the retort. The mean heating value the process is gradually increased from 200°C to 600°C, with limited of the gas is 8.4-12.6 MJ/m3. This gas under war conditions was used admission of air. The products of the processes taking place include, for driving internal combustion engines. in addition to charcoal, a distillate comprising gases and vapours. Liquid distillates, upon collection and settling in tanks, separate The gaseous components include carbon dioxide, carbon monoxide, and form a settled tar layer and a water solution called pyroligneous hydrogen, methane and ethylene. Vapours contain mainly methanol, acid, the latter containing acetic acid, methanol, acetone, methyl acetic acid, acetone, formic acid, propionic aldehyde and acid. They acetate and tar components. After vacuum distillation in multiple- also contain components that condense to form wood tar.
  • Synthesis and Reactions of 4,5-Homotropone and 4,5-Dimethylenetropone Richard Anthony Fugiel Iowa State University

    Synthesis and Reactions of 4,5-Homotropone and 4,5-Dimethylenetropone Richard Anthony Fugiel Iowa State University

    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1974 Synthesis and reactions of 4,5-homotropone and 4,5-dimethylenetropone Richard Anthony Fugiel Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Fugiel, Richard Anthony, "Synthesis and reactions of 4,5-homotropone and 4,5-dimethylenetropone " (1974). Retrospective Theses and Dissertations. 5986. https://lib.dr.iastate.edu/rtd/5986 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]. INFORIVIATIOIM TO USERS This material was produced from a microfilm copy of the original document. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the original submitted. The following explanation of techniques is provided to help you understand markings or patterns which may appear on this reproduction. 1.The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pages to insure you complete continuity. 2. When an image on the film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus cause a blurred image.
  • The Recovery of Ammonia from Waste Organic Substances

    The Recovery of Ammonia from Waste Organic Substances

    . , THESIS: THE RECOVERY OF AMMONIA FROM WASTE ORGANIC SUBSTANCES, - B Y — FRANK H. GAZZOLO, F of trie Degree of Bachelor of Science in College of Science. UNIVERSITY OF ILLINOIS. 1896. ” R E C 0 V E R Y OF A M M 0 N I A FRO M WASTE ORGANIC MATTER." Introduction, Of late years, the immense development of chemical industries can only he accoionted for hy the great advances made in general chemistry,---- particularly in the perfection of .analytical chemistry. It is through scientific research that so many avenues o f industry have been opened. Theoretical and practical chemistry are working side by side to devise means to further the industries and in proportion as chemical knowledge progresses, the technolo­ gies advance. As a natural consequence, the growth of the chemical' industries gave rise to numerous questions as to the technical working. Men are striving to answer these innumer­ able questions by investigation and experimenting, and through these means are due the great advances of chemical technol­ ogy of recent years. The desire to obtain a clear understand­ ing of the original as well as the final products have placed the chemical industries upon a sound chemical basis. ............. ■ ■ ■ ■■■ ............... — ----------------------....................... .........- ......- ............ • ■ ....-.... .......... ... — It is to this desire that scientific chemistry owes so much to technology, fo r much o f the work done in pure chemistry is in response to the demands made upon chemists by the exigencies of the manufactures. It is thus seen that if scientific chemistry has proved itself so necessary for tech­ n ic a l, the la tt e r has likew ise done a great deal to advance the former.
  • Information to Users

    Information to Users

    INFORMATION TO USERS This manuscript has been reproduced 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. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. University Microfilms international A Bell & Howell Information Company 300 North ZeebRoad Ann Arbor Ml 48106-1346 USA 313/761-4700 800 521-0600 Order Number 9427071 The chemistry of polycyclic and spirocyclic compounds Branan, Bruce Monroe, Ph.D. The Ohio State University, 1994 UMI 300 N.ZeebRd. Ann Arbor, MI 48106 THE CHEMISTRY OF POLYCYCLIC AND SPIROCYCLIC COMPOUNDS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University by Bruce Monroe Branan ***** The Ohio State University 1994 Dissertation Committee: Approved by Professor Leo A.
  • Methanol Production – a Technical History a Review of the Last 100 Years of the Industrial History of Methanol Production and a Look Into the Future of the Industry

    Methanol Production – a Technical History a Review of the Last 100 Years of the Industrial History of Methanol Production and a Look Into the Future of the Industry

    http://dx.doi.org/10.1595/205651317X695622 Johnson Matthey Technol. Rev., 2017, 61, (3), 172–182 JOHNSON MATTHEY TECHNOLOGY REVIEW www.technology.matthey.com Methanol Production – A Technical History A review of the last 100 years of the industrial history of methanol production and a look into the future of the industry By Daniel Sheldon Peligot. At a similar time, commercial operations using Johnson Matthey, PO Box 1, Belasis Avenue, destructive distillation were beginning to operate (2). Billingham, Cleveland TS23 1LB, UK There are many parallels between the industrial production of methanol and ammonia and it was the Email: [email protected] early development of the high pressure catalytic process for the production of ammonia that triggered investigations into organic compounds: hydrocarbons, Global methanol production in 2016 was around alcohols and so on. At high pressure and temperature, 85 million metric tonnes (1), enough to fill an Olympic- hydrogen and nitrogen will only form ammonia, however sized swimming pool every twelve minutes. And if all the the story is very different when combining hydrogen global production capacity were in full use, it would only and carbon oxides at high pressure and temperature, take eight minutes. The vast majority of the produced where the list of potential products is lengthy and almost methanol undergoes at least one further chemical all processes result in a mixture of products. Through transformation, more likely two or three before being variations in the process, the catalyst, the conditions, turned into a final product. Methanol is one of the first the equipment or the feedstock, a massive slate of building blocks in a wide variety of synthetic materials industrial ingredients suddenly became available and a that make up many modern products and is also used race to develop commercial processes ensued.
  • Fast Analysis of Coal Tar Polycyclic Aromatic Hydrocarbons on Agilent J&W Select PAH

    Fast Analysis of Coal Tar Polycyclic Aromatic Hydrocarbons on Agilent J&W Select PAH

    Fast analysis of coal tar polycyclic aromatic hydrocarbons on Agilent J&W Select PAH Application Note Author Introduction John Oostdijk The difficulty in analyzing polycyclic aromatic hydrocarbons (PAHs) is the number of Agilent Technologies, Inc. PAHs with the same mass. This makes their separation by GC/MS rather difficult, and so column selectivity and an optimized oven program are necessary for the resolution of PAHs. We describe here the fast analysis of a coal tar sample using an optimized oven program and a 15 m x 0.15 mm x 0.10 µm Select PAH column. Coal tar is a brown or black liquid of high viscosity that smells of naphthalene and aromatic hydrocarbons. It is obtained from the destructive distillation of coal. In the past, coal tar was sourced as a by-product from the manufacture of coal gas but is now produced during the production of coke for steel making. The crude tar contains many organic compounds, such as benzene, naphthalene, methylbenzene and phenols, which can be obtained by distillation, leaving a residue of pitch. At one time coal tar was the major source of organic chemicals, most of which are now derived from petroleum and natural gas. Coal tar pitch is mainly used as binding agent in the production of carbon electrodes, anodes and Søderberg electrodes, for instance, by the aluminium industry. It is also used as a binding agent for refractories, clay pigeons, active carbon, coal briquetting, road construction and roofing. In addition, small quantities are used for heavy-duty corrosion protection. The standard reference material for coal tar analysis (SRM 1597a, NIST) is a natural, combustion-related mixture of PAHs from a medium crude coke-oven tar that is dissolved in toluene.