DOCSLIB.ORG

Thesis Submitted for the Degree of Doctor of Philosophy University of Bath Department of Chemistry 2006

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Thesis Submitted for the Degree of Doctor of Philosophy University of Bath Department of Chemistry 2006 University of Bath PHD Palladium-catalysed C--X bond formations Taylor, Dawn Award date: 2006 Awarding institution: University of Bath Link to publication Alternative formats If you require this document in an alternative format, please contact: [email protected] General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Download date: 04. Oct. 2021 UNIVERSITY OF BATH Palladium-Catalysed C-XBond Formations Dawn Taylor A thesis submitted for the degree of Doctor of Philosophy University of Bath Department of Chemistry 2006 COPYRIGHT Attention is drawn to the fact that copyright of this thesis rests with its author. This copy of the thesis has been supplied on condition that anyone who consults it is understood to recognise that its copyright rests with its author and that no quotation from the thesis and no information derived from it may be published without the prior written consent of the author. This thesis may not be consulted, photocopied or lent to other libraries without the permission of the author for three years from the date of acceptance of the thesis. 17 bC Mcx.^ UMI Number: U220737 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. Dissertation Publishing UMI U220737 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. ProQuest LLC 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 if! SIT Y OF BATH LIBRARY 3C> 1 6 JUL 2007 f h :? .-........... iIn*wwwwsNweiwwweqwwwweBewwei UNIVERSITY OF BATH This work was carried out in collaboration with Pfizer as part o f a CASE studentship. Supervisors: Dr Michael C. Willis, University of Bath Dr Adam T. Gillmore, Pfizer Abstract Abstract Over the last decade palladium catalysed C-X cross-coupling reactions have been developed successfully as a major tool for the synthetic chemist (Chapter 1) and our contribution to this key area of research will be detailed herein. Chapter 2 describes our successful application of palladium catalysis to the formation of new C-0 bonds in the synthesis of aryl enol ethers. Vinyl triflates can be efficiently converted into the corresponding aryl enol ethers by treatment with a phenol, NaOlBu and a catalyst generated from Pd 2 (dba ) 3 and 2-(di-terJ-butylphosphino)biphenyl 3b. Palladium catalysed vinylic C-0 bond formation is the key-step in efficient preparation of a range of substituted aryl enol ethers . 1 Chapter 3 introduces the protocol we have investigated towards the application of palladium catalysed C-0 bond formations to the synthesis of the benzofuran motif. A catalyst generated from Pd 2 (dba ) 3 and DPEphos effects intramolecular C-0 bond formation between enolates and aryl halides in the conversion of 1 -(2 -haloaryl)ketones directly into the corresponding benzofurans. Both cyclic and acyclic ketones are efficient substrates. Thio-ketones can also be employed, allowing the preparation of the corresponding benzothiophenes . 2 Chapter 4 presents our approach towards a novel cascade O-annulation route to the benzofuran motif, establishing a double palladium catalysed C-0 bond forming cross­ coupling reaction. A catalyst generated from Pd 2 (dba ) 3 and 2-(di -tert- butylphosphino)biphenyl 3b in the presence of sodium trimethylsilanoate, acting as both an oxygen donor and base, effects an unusual tandem C-0 bond formation involving an intermolecular alkenyl C-0 bond formation with subsequent aryl C-0 bond formation. The identical reaction can also be achieved in a competitive yield employing a catalyst generated from Pd 2 (dba ) 3 and HPtBu 3 BF4 in the presence of the mild base CS2 CO3 and 2 -tosylethanol as the oxygen donor. Chapter 5 reports the palladium catalysed intramolecular aryl enol ether synthesis from vinyl triflates. Our established catalyst generated from Pd 2 (dba ) 3 and DPEphos with the mild base CS 2 CO3 successfully executes the intramolecular cyclisation of a phenolic oxygen onto an adjacent vinyl triflate group to give the corresponding benzofuran in excellent yield. The analogous thiol cross-coupling reaction can also be achieved to give the corresponding benzothiophene in excellent yield. Preliminary studies towards the Abstract expansion of our O-enolate cyclisation strategy, mentioned earlier, for the formation of six membered ring aryl enol ethers were successful. Chapter 6 gives overall conclusions and outlines the continuing and future work being carried out in this area. Chapter 7 is a formal account of experimental procedures. References (1) Willis, M. C.; Taylor, D.; Gillmore, A. T. Chem. Commun. 2003, 2222-2223. (2) Willis, M. C.; Taylor, D.; Gillmore, A. T. Org. Lett. 2004, 6 ,4755-4757. Contents Contents Abstract i Contents iii Acknowledgements v Abbreviations and Acronyms vi Ligands x Chapter 1 Introduction 1 1.1 Investigation Aims 1 1.2 Desymmetrisation 2 1.3 Resent Results from our Laboratory 2 1.4 Palladium-Catalysis: C-A'Bond Formations 4 1.5 General Catalytic Cycle 6 1.6 Palladium-catalysed Intermolecular C -0 Bond Formations 8 1.7 Palladium-catalysed Intramolecular C -0 Bond Formations 13 1.8 Palladium-catalysed C-S Bond Formations 18 1.9 References 23 Results and Discussion Chapters Chapter 2 Application of Palladium Catalysed C-O Bond Formations to the Synthesis of Enol Ethers 26 2.1 Enol Ethers 26 2.2 Intermolecular Aryl Enol Ethers 32 2.3 Concluding Comments 38 2.4 References 39 Chapter 3 Application of Palladium Catalysed C-O Bond Formations to the Synthesis of the Benzofuran Motif 40 3.1 Synthesis of Benzofuran Motif 40 3.2 Synthesis of Benzothiophene Motif 47 3.3 A Novel OEnolate Cyclisation 49 3.4 Cyclisation and Formation of Benzofurans 56 3.5 Optimisation of Palladium Catalysed a-Arylations 58 3.6 Novel Palladium Catalysed OEnolate Cyclisation 62 3.7 Thio-Ketones to Benzothiophenes 69 3.8 Cyclisation of a-Arylated Cyclopentanone 72 3.9 Indole Strategy 74 3.10 Concluding Observations 76 3.11 References 76 iii Contents Chapter 4 Palladium Catalysed Alkenyl- and Aryl-C-0 Bond Formations: A Cascade O-Annulation Route to the Benzofuran Motif 80 4.1 Proposed Methodology: Tandem Palladium Catalysed C -0 Bond Formations Exploiting an Oxygen Surrogate 80 4.2 Surrogate Chemistry 84 4.3 Discovery of an Oxygen Surrogate Compatible with Palladium Catalysis 91 4.4 Concluding Comments 96 4.5 References 97 Chapter 5 Palladium Catalysed Intramolecular Aryl Enol Ether Synthesis From Vinyl Triflates 99 5.1 Intramolecular Palladium Catalysed Cross-Coupling of Phenols and Vinyl Triflates 99 5.2 Intramolecular Palladium Catalysed Cross-Coupling of Thiols and Vinyl Triflates 105 5.3 Steps Towards an Enantioselective Intramolecular Palladium-Catalysed Synthesis of Aryl Enol Ethers 106 5.4 Extension to O-Enolate Methodology 108 5.5 Concluding Comments 113 5.6 References 113 Chapter 6 Summary and Future Work 115 6.1 Summary 115 6.2 Future Work 115 6.3 References 118 Chapter 7 Experimental 119 7.1 General Experimental 119 7.2 Experimental Analyses 120 Chapter 2 120 Chapter 3 132 Chapter 5 156 7.3 References 179 Appendix 180 Acknowledgements Acknowledgements Many thanks must go first and foremost to my supervisor Mike Willis for all of his advice and guidance throughout the duration of my studies. Also thanks to my industrial supervisor Adam Gillmore for his mentoring both during my placement visit to Pfizer and numerous update meetings. It has been a pleasure working and dining with you both. Thanks to John Lowe, Mark Russell and Chris Chapman (Department of Chemistry, Bath) for their technical NMR and computer support and Inaki Morao, Pfizer, for carrying out the computational studies detailed in this thesis. Pfizer and the EPRSC are also thanked for their financial support. My PhD would never have been the same if it was not for the great people I have met and become friends with including all of the members of the MCW Group both past and present Ai, Ana, Fletch, Gareth, Gary, Helen, Jay, Luke, wee Matt, Phil, Rob, Stav, Steve, Sy and Vincent. A special thanks to Gareth for the useful chemistry discussions and collaboration on the a-arylation chemistry and to Ai, Fletch, Helen, Rob and Sy for proofreading. Also, the then BSc students that had to try to pretend that they were listening to me, Wee Matt and Tim, it was fun! To those doctors/marrieds/wanabes with whom I shared a lab, it has been a pleasure to work with you all especially the girlies Rach, Gan and Ana. And not to forget everyone else in the department, ................your friendship and smiles makes it all worth it. Carly and Belinda, what would I have done without you both? Finally, my family, my surrogate family, my friends and Davy.
Load more

Recommended publications
  • Synthetic Turf Scientific Advisory Panel Meeting Materials
    California Environmental Protection Agency Office of Environmental Health Hazard Assessment Synthetic Turf Study Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019 MEETING MATERIALS THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency Agenda Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019, 9:30 a.m. – 4:00 p.m. 1001 I Street, CalEPA Headquarters Building, Sacramento Byron Sher Auditorium The agenda for this meeting is given below. The order of items on the agenda is provided for general reference only. The order in which items are taken up by the Panel is subject to change. 1. Welcome and Opening Remarks 2. Synthetic Turf and Playground Studies Overview 4. Synthetic Turf Field Exposure Model Exposure Equations Exposure Parameters 3. Non-Targeted Chemical Analysis Volatile Organics on Synthetic Turf Fields Non-Polar Organics Constituents in Crumb Rubber Polar Organic Constituents in Crumb Rubber 5. Public Comments: For members of the public attending in-person: Comments will be limited to three minutes per commenter. For members of the public attending via the internet: Comments may be sent via email to [email protected]. Email comments will be read aloud, up to three minutes each, by staff of OEHHA during the public comment period, as time allows. 6. Further Panel Discussion and Closing Remarks 7. Wrap Up and Adjournment Agenda Synthetic Turf Advisory Panel Meeting May 31, 2019 THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency DRAFT for Discussion at May 2019 SAP Meeting. Table of Contents Synthetic Turf and Playground Studies Overview May 2019 Update .....
    [Show full text]
  • United States Patent Office Paieated Aug
    2,847,458 United States Patent Office Paieated Aug. 2, 1958 2 products of the reaction. Thus it is not surprising that either no structures or incorrect structures have been 2,847,458 assigned to them. Generally these reaction products of the prior art have been reacted with other materials PREPARATION OF ARYLPHOSPHONCACDS such as organic and inorganic bases, metal sulfides, al Tsai H. 'Chao, Somerville, Hans Z. Lecher, Painfield, and cohols, phenols, thiols, aluminum chloride and other Ruth A. Greenwood, Somerville, N. J., assignors to hydrocarbons in order to produce products which were American Cyanamid Company, New York, N. Y., a to be used as additives to mineral oils to prevent cor corporation of Maine rosion or to impart extreme pressure lubricating or de No Drawing. Application March 25, 1955 tergent properties to the oils. Some of these products Serial No. 496,934 have also been proposed as flotation agents. The prior art reaction products of aromatic hydrocar 15 Claims. (Cl. 260-500) bons with phosphorus pentasulfide have never been corn pletely hydrolyzed to form phosphonic acids. Some such This invention relates to a new process of preparing crude reaction products have been blown with steam or arylphosphonic acids. It also relates to arylthionophos nitrogen to remove malodorous thiocompounds which are phine sulfides which are new compounds and are inter formed as by-products. However, the prior art empha mediates in said process. sized that after this treatment the products still contained A number of arylphosphonic acids having the formula substantial amounts of sulfur, that is to say they were ArPO(OH) in which Ar is an aryl radical have been 20 not completely hydrolyzed.
    [Show full text]
  • Thiophosphation of 2-Methyl-2-Nitro-L-Propanol and the Preparation of Monothiophosphoric Acid J
    Journal of Research of the National Bureau of Standards Vol. 48, No. 4, April 1952 Research Paper 2318 Thiophosphation of 2-Methyl-2-Nitro-l-Propanol and the Preparation of Monothiophosphoric Acid J. V. Karabinos, R. A. Paulson, and W. H. Smith The thiophosphation of a nitroalcohol was studied in ether and in pyridine solution. When 2-methyl-2-nitro-l-propanol was refluxed with phosphorus pentasulfide in ether, the corresponding dithiophosphate was formed. In pyridine solution, however, a pyridine salt of the secondary dithiophosphate was formed. A pyridine salt of metatrithophosphoric acid was also isolated from the latter reaction, and this salt was hydrolyzed to pyridinium monothiophosphate. Monothiophosphoric acid monohydrate itself was obtained, for the first time, by application of ion-exchange and lyophilizing techniques to its pyridine salt. 1. Introduction HPS3 + 3H20->H3PS03 + 2H2S. The reaction of phosphorus pentasulfide with The formulas for the pyridinium salts III and IV organic hydroxy compounds reportedly [1 to 4]* may be represented as follows: yields secondary dithiophosphates (I). (C5H5N)2.HPS3. (III). C5H5N.H3PS03. (IV) (RO)2P(S)SH. (I) It is possible that substance III, rather than phos­ An extension of this reaction to a nitroalcohol is phorus pentasulfide, acts as the thiating agent in described. When 2-methyl-2-nitro-l-propanol was pyridine solution [5]. refluxed with phosphorus pentasulfide in ethyl ether, From the mother liquors obtained by the reaction a product melting at 104° G was obtained that gave of phosphorus pentasulfide with the nitroalcohol in elemental analyses and a molecular-weight value pyridine solution, still another crystalline substance .corresponding to 0,0'-bis(2-methyl-2-nitro-propyl-) was obtained; this substance melted at 103° to 104° C dithiophosphate (II).
    [Show full text]
  • 638 Subpart A—Phosphorus Production Subcategory Subpart B
    § 422.10 40 CFR Ch. I (7–1–12 Edition) Subpart A—Phosphorus Subpart D—Defluorinated Production Subcategory Phosphate Rock Subcategory § 422.10 Applicability; description of SOURCE: 41 FR 25975, June 23, 1976, unless the phosphorus production sub- otherwise noted. category. The provisions of this subpart are ap- § 422.40 Applicability; description of plicable to discharges of pollutants re- the defluorinated phosphate rock sulting from the production of phos- subcategory. phorus and ferrophosphorus by smelt- The provisions of this subpart are ap- ing of phosphate ore. plicable to discharges resulting from the defluorination of phosphate rock Subpart B—Phosphorus by application of high temperature treatment along with wet process phos- Consuming Subcategory phoric acid, silica and other reagents. § 422.20 Applicability; description of the phosphorus consuming sub- § 422.41 Specialized definitions. category. For the purpose of this subpart: The provisions of this subpart are ap- (a) Except as provided below, the gen- plicable to discharges of pollutants re- eral definitions, abbreviations, and sulting from the manufacture of phos- methods of analysis set forth in 40 CFR phoric acid, phosphorus pentoxide, part 401 shall apply to this subpart. (b) The term phosphorus pentasulfide, phosphorus process waste water means any water which, during manu- trichloride, and phosphorus facturing or processing, comes into di- oxychloride directly from elemental rect contact with or results from the phosphorus. The production of phos- production or use of any raw material, phorus trichloride and phosphorus intermediate product, finished product, oxychloride creates waste water pollut- by-product, or waste product. The term ants not completely amenable to the ‘‘process waste water’’ does not include procedures utilized for best practicable contaminated nonprocess waste water, control technology currently available.
    [Show full text]
  • Homogeneous Models of Thiophene Hds Reactions
    HOMOGENEOUS MODELS OF THIOPHENE HDS REACTIONS. SELECTIVITY IN THIOPHENE C-S CLEAVAGE AND THIOPHENE REACTIONS WITH DINUCLEAR METAL COMPLEXES. William D. Jones,* David A. Vicic, R. Martin Chin, James H. Roache, and Andy W. Myers. Department of Chemistry, University of Rochester, Rochester, NY 14627 Received August 1, 1996 - Abstract: The reactive 16 e metal fragment [(C5Me5)Rh(PMe3)] inserts into a wide variety of thiophene C-S bonds. The structures of the thiophene, benzothiophene, and dibenzothiophene insertion complexes have been determined. While the thiophene complex adopts a planar 6- membered ring structure the other metallacycles are bent, and all molecules possess localized diene structures. The mechanism of C-S cleavage was found to proceed by way of initial sulfur coordination. 2-Methylbenzothiophene gives a kinetic product resulting from cleavage of the sulfur-vinyl bond, but then rearranges to cleave the sulfur-aryl bond. A number of substituted dibenzothiophenes were examined, showing little electronic effect of substituents, but showing a large steric effect of substituents at the 4 and 6 positions. 4,6-Dimethyldibenzothiophene does not undergo cleavage, but instead forms an S-bound complex. Reactions of a cobalt analog, (C5Me5)Co(C2H4)2 with thiophenes also lead to C-S cleaved products, and the use of a dinuclear iridium system produces a butadiene complex in which both C-S bonds have been cleaved. Introduction of these sulfur containing compounds prior to The hydrodesulfurization of petroleum is one treatment. Figure 2 shows how this original mixture of several steps in the hydrotreating of oil in which of compounds is changed upon HDS treatment at sulfur is removed from thiols and thiophenes as temperatures of 350 - 390 °C.
    [Show full text]
  • China's Role in the Chemical and Biological Disarmament Regimes
    ERIC CRODDY China’s Role in the Chemical and Biological Disarmament Regimes ERIC CRODDY Eric Croddy is a Senior Research Associate at the Chemical and Biological Weapons Nonproliferation Program, Center for Nonproliferation Studies, Monterey Institute of International Studies. He is the author of Chemical and Biological Warfare: A Comprehensive Survey for the Concerned Citizen (New York: Copernicus Books, 2001). odern China has been linked with the prolif- least—and with considerable diplomatic effort—China eration of nuclear, chemical, and missile weap- broadcasts its commitment to both the CWC and the Mons technology to states of proliferation con- BWC. cern, and its compliance with arms control and disarma- Few unclassified publications analyze the role that CBW ment is seen as key to the effectiveness of weapons of have played in Chinese military strategy, nor is much in- 1 mass destruction (WMD) nonproliferation efforts. In this formation available on Beijing’s approach to negotiating context, the answer to Gerald Segal’s question, “Does CBW disarmament treaties. This is not surprising: China 2 China really matter?” is most definitely, “Yes.” In the is an extremely difficult subject for study where sensitive realm of chemical and biological weapons (CBW), military matters are concerned. A 1998 report by Dr. Bates Beijing’s role is closely linked to its view of the multilat- Gill, Case Study 6: People’s Republic of China, published eral disarmament regimes for CBW, namely the Chemi- by the Chemical and Biological Arms Control Institute, cal Weapons Convention (CWC) and the Biological and was the first to seriously address the issue of China and Toxin Weapons Convention (BWC), and of related mul- CBW proliferation.
    [Show full text]
  • Figure: 30 TAC §335.521(A)(2) [Figure: 30 TAC §335.521(A)(2)]
    Figure: 30 TAC §335.521(a)(2) [Figure: 30 TAC §335.521(a)(2)] Appendix 1, Table 2. Examples of Ignitable Solids. Constituents listed from Department of Transportation Regulations, 49 CFR Part 173 Subpart E, October 1, 1993. (Note: The presence of a constituent on this table in a nonhazardous [non-hazardous] waste does not automatically identify that waste as a Class 1 ignitable waste. The constituents on this table are examples of materials which could be considered Class 1 ignitable waste. The physical characteristics of the waste will be the determining factor as to whether or not a waste is ignitable. Refer to §335.505(2) of this title (relating to Class 1 Waste Determination) for the Class 1 ignitable criteria.) Compound or Material Aluminum, metallic, powder Alkali metal amalgams Alkali metal amides Aluminum alkyl halides Aluminum alkyl hydrides Aluminum alkyls Aluminum borohydrides Aluminum carbide Aluminum ferrosilicon powder Aluminum hydride Aluminum phosphide Aluminum resinate Aluminum silicon powder Ammonium picrate 2, 2'-Azodi-(2,4-dimethyl-4-methoxyvaleronitrile) 2, 2'-Azodi-(2,4-dimethylvaleronitrile) 1, 1' Azodi-(hexahydrobenzonitrile) 2,2'-Azodi (2-methyl-butryronitrile) Azodiisobutryonitrile Barium, metallic Barium alloys, pyrophoric Barium azide Benzene-1,3-disulfohydrazide Benzene sulfohydrazide 4-(Benzyl(ethyl)amino)-3-ethoxybenzenediazonium zinc chloride 4-(Benzyl(methyl)amino)-3-ethoxybenzenediazonium zinc chloride Borneol Boron trifluoride dimethyl etherate 5-tert-Butyl-2,4,6-trinitro-m-xylene Calcium, metallic Calcium
    [Show full text]
  • Dibenzothiophene (DBT), and Carbazole (CA) from Benzofuran (BF), Benzothiophene (BT), and Indole (IN) with Cyclopentadienyl Radical
    International Journal of Molecular Sciences Article The Gas-Phase Formation Mechanism of Dibenzofuran (DBF), Dibenzothiophene (DBT), and Carbazole (CA) from Benzofuran (BF), Benzothiophene (BT), and Indole (IN) with Cyclopentadienyl Radical 1, 1, 1,2 1 1,2, 3 Xuan Li y, Yixiang Gao y, Chenpeng Zuo , Siyuan Zheng , Fei Xu *, Yanhui Sun and Qingzhu Zhang 1 1 Environment Research Institute, Shandong University, Qingdao 266237, China; [email protected] (X.L.); [email protected] (Y.G.); [email protected] (C.Z.); [email protected] (S.Z.); [email protected] (Q.Z.) 2 Shenzhen Research Institute, Shandong University, Shenzhen 518057, China 3 College of Environment and Safety Engineering, Qingdao University of Science & Technology, Qingdao 266042, China; [email protected] * Correspondence: [email protected]; Tel.: +86-532-58631992 These authors contributed equally to this article. y Received: 11 August 2019; Accepted: 28 October 2019; Published: 31 October 2019 Abstract: Benzofuran (BF), benzothiophene (BT), indole (IN), dibenzofuran (DBF), dibenzothiophene (DBT), and carbazole (CA) are typical heterocyclic aromatic compounds (NSO-HETs), which can coexist with polycyclic aromatic hydrocarbons (PAHs) in combustion and pyrolysis conditions. In this work, quantum chemical calculations were carried out to investigate the formation of DBF, DBT, and CA from the reactions of BF, BT, and IN with a cyclopentadienyl radical (CPDyl) by using the hybrid density functional theory (DFT) at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants of crucial elementary steps were deduced over 600 1200 K, using canonical − variational transition state theory with a small-curvature tunneling contribution (CVT/SCT).
    [Show full text]
  • Hydrogenation of 2-Methylnaphthalene in a Trickle Bed Reactor Over Bifunctional Nickel Catalysts
    The University of Maine DigitalCommons@UMaine Electronic Theses and Dissertations Fogler Library Fall 12-2020 Hydrogenation of 2-methylnaphthalene in a Trickle Bed Reactor Over Bifunctional Nickel Catalysts Matthew J. Kline University of Maine, [email protected] Follow this and additional works at: https://digitalcommons.library.umaine.edu/etd Part of the Catalysis and Reaction Engineering Commons, and the Petroleum Engineering Commons Recommended Citation Kline, Matthew J., "Hydrogenation of 2-methylnaphthalene in a Trickle Bed Reactor Over Bifunctional Nickel Catalysts" (2020). Electronic Theses and Dissertations. 3284. https://digitalcommons.library.umaine.edu/etd/3284 This Open-Access Thesis is brought to you for free and open access by DigitalCommons@UMaine. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of DigitalCommons@UMaine. For more information, please contact [email protected]. HYDROGENATION OF 2-METHYLNAPHTHALENE IN A TRICKLE BED REACTOR OVER BIFUNCTIONAL NICKEL CATALYSTS By Matthew J. Kline B.S. Seton Hill University, 2018 A THESIS Submitted in Partial Fulfillment of the Requirements For the Degree of Master oF Science (in Chemical Engineering) The Graduate School The University of Maine December 2020 Advisory Committee: M. Clayton Wheeler, Professor of Chemical Engineering, Advisor Thomas J. Schwartz, Assistant ProFessor oF Chemical Engineering William J. DeSisto, ProFessor oF Chemical Engineering Brian G. Frederick, ProFessor oF Chemistry
    [Show full text]
  • Jacqueline Garland Phd Thesis
    STUDIES IN PHOSPHORUS-SELENIUM CHEMISTRY Jacqueline Garland A Thesis Submitted for the Degree of PhD at the University of St Andrews 2013 Full metadata for this item is available in Research@StAndrews:FullText at: http://research-repository.st-andrews.ac.uk/ Please use this identifier to cite or link to this item: http://hdl.handle.net/10023/3688 This item is protected by original copyright Studies in Phosphorus-Selenium Chemistry Jacqueline Garland This thesis is submitted in partial fulfilment for the degree of Doctor of Philosophy (PhD.) at the University of St Andrews and Doctor rerum naturalium (Dr. rer. nat.) at the Universität Leipzig 21st February 2013 Supervisors: Prof. J. D. Woollins Prof. E Hey-Hawkins Declarations I, Jacqueline Garland, hereby certify that this thesis, which is approximately 53000 words in length, has been written by me, that it is the record of work carried out by me and that it has not been submitted in any previous application for a higher degree. I was admitted as a research student in September, 2008 and as a candidate for the degree of July 2009; in the higher study for which this is a record was carried out in the University of St Andrews and the Universität Leipzig between 2008 and 2013. Date: 21st February 2013 Signature of candidate: I hereby certify that the candidate has fulfilled the conditions of the Resolution and Regulations appropriate for the degree of PhD. in the University of St Andrews and that the candidate is qualified to submit this thesis in application for that degree. Date: 21st February 2013 Signature of supervisor: I hereby certify that the candidate has fulfilled the conditions of the Resolution and Regulations appropriate for the degree of Dr.
    [Show full text]
  • Synthesis and Electropolymerization of Furan End−Capped Dibenzothiophene/Dibenzofuran and Electrochromic Properties of Their Polymers
    Int. J. Electrochem. Sci., 12 (2017) 5000 – 5011, doi: 10.20964/2017.06.29 International Journal of ELECTROCHEMICAL SCIENCE www.electrochemsci.org Synthesis and Electropolymerization of Furan End−capped Dibenzothiophene/Dibenzofuran and Electrochromic Properties of Their Polymers Hua Gu1‡, Kaiwen Lin2‡, Hongtao Liu3, Nannan Jian3, Kai Qu3, Huimin Yu3, Jun Wei3, Shuai Chen1,4,* and Jingkun Xu1,4,* 1School of Pharmacy, Jiangxi Science & Technology Normal University, Nanchang 330013, PR China 2School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641, PR China 3School of Chemistry & Chemical Engineering, Jiangxi Science & Technology Normal University, Nanchang 330013, PR China; 4Jiangxi Engineering Laboratory of Waterborne Coatings, Nanchang 330013, PR China *E−mail: [email protected], [email protected] ‡ These authors contributed equally to this work. Received: 20 January 2017 / Accepted: 18 April 2017 / Published: 12 May 2017 Two furan end−capped dibenzo five−membered ring monomers, 2,8−bis−(furan−2−yl)−dibenzothiophene (DBT−Fu) and 2,8−bis−(furan−2−yl)−dibenzofuran (DBF−Fu) were successfully synthesized via Stille couple reaction. Corresponding polymers, P(DBT−Fu) and P(DBF−Fu), were obtained by employed the electropolymerization. The surface morphology, electrochemical and optical properties of monomers and polymers were researched by cyclic voltammetry (CV), scanning electron microscopy (SEM), and UV−via spectra method. Both polymers exhibited obvious color changes from neutral state
    [Show full text]
  • Kinetics of Hydrodesulfurization of Dibenzothiophene on Sulfided Commercial Co-Mo/Γ-Al2o3catalyst IOةŸ ل
    The Journal of Engineering Research Vol. 3, No. 1 (2006) 38-42 Kinetics of Hydrodesulfurization of Dibenzothiophene on Sulfided Commercial Co-Mo/γ-Al2O3 Catalyst Y.S. Al-Zeghayer1 and B.Y. Jibril*2 1Chemical Engineering Department, King Saud University, P.O. Box 800, Riyadh 11421, Saudi Arabia 2Petroleum and Chemical Engineering Department, Sultan Qaboos University, P.O. Box 33, Al-Khoud, PC 123, Muscat, Oman Received 27 April 2005; accepted 17 September 2005 …QÉŒ »àjÈc …õØM πeÉY ≈∏Y dibenzothiophene IOÉŸ á«æ«Lh~«¡dG âjȵdG ádGPG äÓYÉØJ á«côM 2@πjÈL .….Ü h 1ÒgõdG .¢S.… á≤∏£e áLQO 683 ¤G 633 ÚH Ée ájQGôM äÉLQO ~æY …QÉŒ »àjÈc …õØM πeÉY ≈∏Y É«∏ª©e â°SQhO dibenzothiophene IOÉŸ á«æ«LhQ~«¡dG âjȵdG ádGPEG äÓYÉØJ áÑ«côJ :á°UÓÿG á«∏ª©ŸG èFÉàædG §Ñæà°ùj ¿G øµÁ áHPɵdG ¤h’G áLQ~dG øe »°VÉjQ êPƒ‰ ¿G âÑKG .âe~îà°SG á«æ«LhQ~«¡dG âjȵdG ádGPGC á«∏ªY øe É¡«∏Y π°UÉ◊G DBT IOÉŸ áØ«©°V äGõ«côJ .…ƒL §¨°V 10 ~æY h (CHB) ɢª˘g ɢ¡˘«˘∏˘Y ∫ƒ˘°üÙG ᢫˘˘°ù«˘˘Fô˘˘dG äɢ˘é˘˘à˘˘æŸG ¿G ~L,, 51.7 kcal/mol …hɢ°ùJ ɢ¡˘fG ~˘˘Lh DBT IOÉe π˘jƒ˘ë˘à˘d á˘£˘°ûæŸG á˘bɢ£˘dG .ᢵ˘∏˘¡˘à˘°ùŸG DBT IOɢ˘Ÿ »£©J á©HÉààŸG ájRGƒàŸG äÓYÉØàdG ¿G ~Lhh .âHôL á©HÉààŸG ájRGƒàŸGh …RGƒàŸG äÓYÉØàdG ɪgh äÓYÉØàdG áµÑ°T øe ÚæKG ¿Gh . Biphenyl (BP) and cyclohexylbenzene (EBP) BP IOÉe ¤G DBT IOÉe πjƒëàd ᣰûæŸG ábÉ£dG º«b ¿G .IQGô◊G áLQO ≈∏Y ~ªà©J CHBIOÉe ¤G BP IOÉe áÑ°ùf ¿Gh .
    [Show full text]