Hydrocarbon Processing Overview
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Transition-Metal Catalyzed Synthesis of Carbonyl Compounds Using Formates Or Formamides As Carbonyl Sources
Journal of the Japan Petroleum Institute, 61, (1), 1-9 (2018) 1 [Review Paper] Transition-metal Catalyzed Synthesis of Carbonyl Compounds Using Formates or Formamides as Carbonyl Sources Tetsuaki FUJIHARA and Yasushi TSUJI* Dept. of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, JAPAN (Received August 24, 2017) Various available approaches for catalytic carbonylation reactions using formates and formamides with transi- tion metal catalysts are reviewed. Pd complexes catalyze the hydroesterification or hydrocarbamoylation of alkynes using aryl formates or formamides, respectively, as the carbonyl sources. The esterification of aryl halides with aryl formates proceeds in the presence of a Pd catalyst with suitable ligands. Using a Cu complex with a bulky bidentate phosphine ligand is used as a catalyst, boraformylation and silaformylation of allenes effi- ciently proceeds using alkyl formates as a formyl source. Keywords Formate, Formamide, Homogeneous catalysis, Palladium, Copper 1. Introduction This review describes Pd-catalyzed hydroesterifica- tion and hydrocarbamoylation of alkynes employing Carbon monoxide (CO) is an important C1 unit which formates or formamides as the carbonyl sources, is often used as a carbonyl source to convert various respectively. Esterification of aryl halides with aryl bulk chemicals into functionalized products in large- formates also proceeds in the presence of a Pd catalyst. scale application for industrial syntheses1)~3). Cu-catalyzed bora- and silaformylation of allenes em- However, carbonylation reactions with CO are not typi- ploying an alkyl formate is also possible. The scope cally used in the laboratory-scale synthesis of complex of substrates and plausible reaction mechanisms are dis- organic molecules, probably due to general reluctance cussed. -
Part I: Carbonyl-Olefin Metathesis of Norbornene
Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate School of Arts and Sciences COLUMBIA UNIVERSITY 2016 1 © 2016 Zara Maxine Seibel All Rights Reserved 2 ABSTRACT Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel This thesis details progress towards the development of an organocatalytic carbonyl- olefin metathesis of norbornene. This transformation has not previously been done catalytically and has not been done in practical manner with stepwise or stoichiometric processes. Building on the previous work of the Lambert lab on the metathesis of cyclopropene and an aldehyde using a hydrazine catalyst, this work discusses efforts to expand to the less stained norbornene. Computational and experimental studies on the catalytic cycle are discussed, including detailed experimental work on how various factors affect the difficult cycloreversion step. The second portion of this thesis details the use of chiral cyclopropenimine bases as catalysts for asymmetric Michael reactions. The Lambert lab has previously developed chiral cyclopropenimine bases for glycine imine nucleophiles. The scope of these catalysts was expanded to include glycine imine derivatives in which the nitrogen atom was replaced with a carbon atom, and to include imines derived from other amino acids. i Table of Contents List of Abbreviations…………………………………………………………………………..iv Part I: Carbonyl-Olefin Metathesis…………………………………………………………… 1 Chapter 1 – Metathesis Reactions of Double Bonds………………………………………….. 1 Introduction………………………………………………………………………………. 1 Olefin Metathesis………………………………………………………………………… 2 Wittig Reaction…………………………………………………………………………... 6 Tebbe Olefination………………………………………………………………………... 9 Carbonyl-Olefin Metathesis……………………………………………………………. -
S Via Ring-Opening Metathesis Polymerization (ROMP)
1 Chapter 1 Synthesis of End-Functionalized Polynorbornenes via Ring-Opening Metathesis Polymerization (ROMP) 2 Abstract The synthesis of a variety of polynorbornenes (PNB)s bearing acetoxy, hydroxy, and vinyl end-groups was accomplished. PNBs with an acetoxy group at one terminus and a vinyl group at the other were prepared using norbornene, ruthenium-based olefin metathesis catalyst (PCy3)2Cl2Ru=CHPh, and allyl acetate as a chain transfer agent (CTA). Employing a more active catalyst, (1,3-dimesityl-4,5-dihydroimidazol-2- ylidene)(PCy3)Cl2Ru=CHPh, and 1,4-diacetoxy-2-butene as the CTA afforded telechelic PNBs bearing acetoxy groups at both ends of the polymer chains. Molecular weights were controlled by varying the initial monomer/CTA ratio and were in agreement with their theoretical values. Using a similar procedure, acetoxy end-functionalized PNBs were also obtained by degradation of high molecular weight PNB. Removal of the acetoxy groups afforded the corresponding hydroxy terminated polymers with number averaged functionalities close to two. Mechanisms are proposed for the formation of the end-functionalized polymers. Correction factors for characterizing PNBs by gel- permeation chromatography (GPC) are also suggested. Portions of this chapter have been previously reported, see: Bielawski, C. W.; Benitez, D.; Morita, T.; Grubbs, R. H. Macromolecules 2001, 34, 8610. 3 Introduction Telechelic polymers, or polymers with functional groups selectively positioned at the termini of any given chain, have been extensively employed in a variety of applications including intermediates in the synthesis of block copolymers, use as cross- linking agents, and in the formation of polymeric networks.1-4 Since these applications are often dependent on structural, mechanical, and thermal properties of the telechelic polymer, expanding the range of selectable monomers remains a synthetic goal in polymer chemistry. -
The Synthetization and Analysis of Dicyclopentadiene and Ethylidene-Norbornene Microcapsule Systems
polymers Article The Synthetization and Analysis of Dicyclopentadiene and Ethylidene-Norbornene Microcapsule Systems Ionut Sebastian Vintila 1,2,*, Horia Iovu 2, Andreea Alcea 1, Andreia Cucuruz 3, Andrei Cristian Mandoc 1 and Bogdan Stefan Vasile 4 1 National Research and Development Institute for Gas Turbines COMOTI, 061126 Bucharest, Romania; [email protected] (A.A.); [email protected] (A.C.M.) 2 Department of Bioresources and Polymer Science, Faculty of Applied Chemistry and Materials Science, University Politehnica of Bucharest, 011061 Bucharest, Romania; [email protected] 3 Department of Science and Engineering of Oxide Materials and Nanomaterials, Faculty of Applied Chemistry and Materials Science, University Politehnica of Bucharest, 011061 Bucharest, Romania; [email protected] 4 National Research Centre for Micro and Nanomaterials, Faculty of Applied Chemistry and Materials Science, University POLITEHNICA of Bucharest, 060042 Bucharest, Romania; [email protected] * Correspondence: [email protected]; Tel.: +40-726998218 Received: 7 April 2020; Accepted: 25 April 2020; Published: 4 May 2020 Abstract: The activities of this paper were focused on an in-situ fabrication process for producing two self-healing systems containing dicyclopentadiene and 5-ethylidene-2-norbornene monomers encapsulated in a urea-formaldehyde shell and integration methods applied in the epoxy matrix to analyse and compare the influences of their integration into the neat epoxy matrix. The self-healing systems were first synthesized according to a literature review, and subsequently, an optimization process was conducted for the fabrication process. Neat epoxy specimens were fabricated as reference specimens and subjected to flexural tests. Several integration methods for incorporating the self-healing systems into the epoxy resin were investigated. -
Designing Polymers for Advanced Battery Chemistries
REVIEWS Designing polymers for advanced battery chemistries Jeffrey Lopez 1, David G. Mackanic 1, Yi Cui 2,3 and Zhenan Bao 1* Abstract | Electrochemical energy storage devices are becoming increasingly important to our global society , and polymer materials are key components of these devices. As the demand for high- energy density devices increases, innovative new materials that build on the fundamental understanding of physical phenomena and structure–property relationships will be required to enable high-capacity next-generation battery chemistries. In this Review , we discuss core polymer science principles that are used to facilitate progress in battery materials development. Specifically , we discuss the design of polymeric materials for desired mechanical properties, increased ionic and electronic conductivity and specific chemical interactions. We also discuss how polymer materials have been designed to create stable artificial interfaces and improve battery safety. The focus is on these design principles applied to advanced silicon, lithium-metal and sulfur battery chemistries. The development of new electrochemical energy storage of existing materials or to enable the application of new technologies has been instrumental to the proliferation battery chemistries. In this Review, we summarize the of portable electronic devices and the increasing adop- fundamental polymer science and engineering con- tion of electric vehicles. Intermittent electricity genera- cepts related to the development of polymers for next- tion (for example, from wind and solar power sources) generation battery applications (Table 1). We specifically has further intensified the demand for high-energy den- discuss how these core concepts drive the design of new sity, high- power and low-cost energy storage devices1,2. -
Revised Group Additivity Values for Enthalpies of Formation (At 298 K) of Carbon– Hydrogen and Carbon–Hydrogen–Oxygen Compounds
Revised Group Additivity Values for Enthalpies of Formation (at 298 K) of Carbon– Hydrogen and Carbon–Hydrogen–Oxygen Compounds Cite as: Journal of Physical and Chemical Reference Data 25, 1411 (1996); https://doi.org/10.1063/1.555988 Submitted: 17 January 1996 . Published Online: 15 October 2009 N. Cohen ARTICLES YOU MAY BE INTERESTED IN Additivity Rules for the Estimation of Molecular Properties. Thermodynamic Properties The Journal of Chemical Physics 29, 546 (1958); https://doi.org/10.1063/1.1744539 Critical Evaluation of Thermochemical Properties of C1–C4 Species: Updated Group- Contributions to Estimate Thermochemical Properties Journal of Physical and Chemical Reference Data 44, 013101 (2015); https:// doi.org/10.1063/1.4902535 Estimation of the Thermodynamic Properties of Hydrocarbons at 298.15 K Journal of Physical and Chemical Reference Data 17, 1637 (1988); https:// doi.org/10.1063/1.555814 Journal of Physical and Chemical Reference Data 25, 1411 (1996); https://doi.org/10.1063/1.555988 25, 1411 © 1996 American Institute of Physics for the National Institute of Standards and Technology. Revised Group Additivity Values for Enthalpies of Formation (at 298 K) of Carbon-Hydrogen and Carbon-Hydrogen-Oxygen Compounds N. Cohen Thermochemical Kinetics Research, 6507 SE 31st Avenue, Portland, Oregon 97202-8627 Received January 17, 1996; revised manuscript received September 4, 1996 A program has been undertaken for the evaluation and revision of group additivity values (GAVs) necessary for predicting, by means of Benson's group additivity method, thermochemical properties of organic molecules. This review reports on the portion of that program dealing with GAVs for enthalpies of formation at 298.15 K (hereinafter abbreviated as 298 K) for carbon-hydrogen and carbon-hydrogen-oxygen compounds. -
Technical Notes
Technical notes New tools to manage common taint problems Wine producers can proactively manage potential taint issues through a new set of tools available from the AWRI Analytical Service. In recent years, several taint problems have occurred in Australia resulting in serious financial consequences for the wine producers involved. The AWRI provides assistance in resolving these issues and we continue to develop services that enable winemakers and suppliers to proactively reduce the risk of wine contamination. The implementation of preventative measures and controls can minimise the development of taints. A broad suite of analytical services tailored for QC testing for the presence of taints in winemaking additives, closures and oak products as well as taint assessment of juices and wines is available through the Analytical Service. Recently, we have also developed a new sensory training tool to help winemakers recognise the most common taints. Minimising risk Early identification of the potential sources of contamination is critical. Testing of additives and juices/wines at critical control points proactively detects and eliminates any taints before they develop into a problem. Just like taking out insurance it comes with a small price tag compared to the risk of losing large volumes of wines due to serious taint problems. Also, in today’s highly competitive market, the purchase of just one slightly tainted bottle of wine can be enough to influence a consumer to seek an alternative brand or label. So, it is crucial to have the ability to monitor and prevent taint and, if necessary, treat wines to prevent further tainting. Analytical services to prevent and control taint problems This article provides detailed information on three examples of commercial taint services developed by the AWRI Analytical Service in collaboration with staff at the AWRI and our stakeholders. -
Unlted States Patent [19] [11] Patent Number: 4,816,521 Asrar [45] Date of Patent: Mar
Unlted States Patent [19] [11] Patent Number: 4,816,521 Asrar [45] Date of Patent: Mar. 28, 1989 [54] CY CLOPENTADIENYLENE VINYLENE 4,022,954 5/1977 Kurosawa et a1. ........... .. 525/366 X POLYMERS 4,316,978 2/1982 Kennedy et a1. .. 526/348.7 4,412,044 10/1983 Takahashi et a1. ........... .. 525/366 X [75] Inventor: Jawed Asrar, Wilbraham, Mass. FOREIGN PATENT DOCUMENTS [73] Assignee: Monsanto Company, St. Louis, Mo. [21] Appl. No.: 54,633 3224159 12/1983 Fed. Rep. of Germany_ 525/3272 _ Primary Examiner—Edward J. Snuth, Jr. [221 Flled‘ May 27’ 1987 Assistant Examiner-F. M. Teskin [s1] rm. cu ........................ .. cosr 32/04; C08F 8/00 Amine» Agent, or Firm-Thomas E- Kelley; William J [52] US. Cl. ............................ .. 525/3273; 525/3295; Famngton 525/326.1; 525/366; 526/280; 526/281; 7 TR, 526/269; 428/409; 428/411.1; 264/33l.17 [5 ] _ ABS _ Cr _ _ ' [58] Field of Search ............................. .. 526/269, 281; Polycyclopentadlenylene vmylene exhlbltmg Solvent 525/3273, 328.6, 329.5, 366, 327.2; 428/523, resistance, e.g. to chlorinated solvents such as chloro 409, 411,1; 264/331,17 form and methylene chloride and to amine solvents . such as dimethylformamide, is prepared by removal of [56] References cued acid groups from precursor polymer having norbornene U.S. PATENT DOCUMENTS dioxo derivatives. 3,330,815 7/1967 McKeon et a1. ................. .. 260/93.1 3,959,234 5/ 1976 Kurosawa et a1. ................. .. 260/78 4 Claims, N0 Drawings 4,816,521 1 2 CYCLOPENTADIENYLENE VINYLENE POLYMERS CH=CH— BACKGROUND OF THE INVENTION 5 Disclosed herein are conjugated polymers, e.g. -
Cycloolefin Copolymers: Processing, Properties Application
Cycloolefin copolymers: Processing, Properties Application Petr Mlejnek Bachelor Thesis 2007 ABSTRACT The main object of this bachelor thesis is to compile the complex review of preparation, chemical structure, morphology, properties, processing and applica- tion of cyclic olefin copolymers. Recently, these modern materials have attracted the attention of the researchers as well as plastic processors. Cyclic olefin co- polymers are prepared by copolymerization of cyclic and linear olefins. By varying the structure, they can be tailored for specific applications. Generally, they are characterized by almost amorphous structure, high glass transition temperature, high transparency and low density. Presently, they are successfully applied in packaging and pharmaceutics ANOTACE Hlavním úelem této bakaláské práce je sestavit pehlednou literární re- šerši týkající se výroby, chemické struktury, morfologie, vlastností, zpracování a aplikací cyklických olefinických kopolymer. V poslední dob jsou tyto moderní materiály pedmtem zájmu jak výzkumných tým, tak pedevším zpracovatel plast. Cyklické olefinické kopolymery se vyrábjí kopolymerací cyklických a line- árních olefin. Zmnou struktury lze vyrábt tzv. materiály na míru pro specifické aplikace. Obecn jsou charakterizovány tém zcela amorfní strukturou, vysokou teplotou skelného pechodu, vysokou prhledností a nízkou hustotou. V souasné dob se s úspchem využívají pro výrobu obal a farmaceutických pomcek. ACKNOWLEDGEMENTS I would like to thank my supervisor Jana Výchopová for her professional help, -
Forcing Single-Chain Nanoparticle Collapse Through Hydrophobic Solvent Interactions in Comb Copolymers
Polymer Chemistry View Article Online COMMUNICATION View Journal | View Issue Forcing single-chain nanoparticle collapse through hydrophobic solvent interactions in Cite this: Polym. Chem., 2020, 11, 292 comb copolymers† Received 16th August 2019, Accepted 4th October 2019 Cheyenne H. Liu, ‡ Logan D. Dugas,‡ Jared I. Bowman, Tamuka Chidanguro, DOI: 10.1039/c9py01235d Robson F. Storey and Yoan C. Simon * rsc.li/polymers We introduce a novel synthetic strategy in which high molecular crosslinks are reminiscent of disulfide bridges, and the intro- weight comb copolymers with aliphatic side chains can collapse duction of catalytic sites is comparable to active enzymatic into single-chain nanoparticles (SNCPs) via photodimerization of pockets.6,17,18 Consequently, the scientific pursuit of SCNPs – anthracene under ultraviolet (UV) irradiation. By deliberately has grown unabated in areas such as catalysis,17,19 21 – – selecting hydrophobic comonomers with disparate solvency, we sensing,22 24 and site-specific drug delivery.25 27 demonstrated that we could control chain collapse. We attribute To realize the full potential of SCNPs, one must understand these results to the formation of pseudo-unimicellar structures, the parameters governing chain collapse. Seminal work by whereby polyisobutylene (PIB) side chains are preferentially sol- Pomposo and coworkers laid the theoretical framework for the vated, thereby compressing anthracene moieties to form a denser understanding of how solvent selection affects the ultimate – crosslinked core. The control of hydrophobic interactions is a size and structure of SCNPs.28 31 They meticulously explored common occurrence in proteins and we believe that our approach through computational modeling whether SCNPs can form – can be further extended to achieve multi-compartment SCNPs true globular structures.28,29,31 33 Namely, they showed that whereby each section is responsible for a given function. -
Molecular Encapsulation in Kinetically Trapped, Hydrogen-Bonded Pyrogallolarene Hexamers
University of Denver Digital Commons @ DU Electronic Theses and Dissertations Graduate Studies 6-1-2014 Molecular Encapsulation in Kinetically Trapped, Hydrogen-Bonded Pyrogallolarene Hexamers Jennifer Christine Chapin Lake University of Denver Follow this and additional works at: https://digitalcommons.du.edu/etd Part of the Organic Chemistry Commons Recommended Citation Chapin Lake, Jennifer Christine, "Molecular Encapsulation in Kinetically Trapped, Hydrogen-Bonded Pyrogallolarene Hexamers" (2014). Electronic Theses and Dissertations. 120. https://digitalcommons.du.edu/etd/120 This Dissertation is brought to you for free and open access by the Graduate Studies at Digital Commons @ DU. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of Digital Commons @ DU. For more information, please contact [email protected],[email protected]. MOLECULAR ENCAPSULATION IN KINETICALLY TRAPPED, HYDROGEN-BONDED PYROGALLOLARENE HEXAMERS __________ A Dissertation Presented to the Faculty of Natural Sciences and Mathematics University of Denver __________ In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy __________ by Jennifer Christine Chapin Lake June 2014 Advisor: Byron W. Purse ©Copyright by Jennifer Christine Chapin Lake 2014 All Rights Reserved Author: Jennifer Christine Chapin Lake Title: MOLECULAR ENCAPSULATION IN KINETICALLY TRAPPED, HYDROGEN-BONDED PYROGALLOLARENE HEXAMERS Advisor: Byron W. Purse Degree Date: June 2014 Abstract Pyrogallolarene and resorcinarene hexamers are hydrogen-bonded capsules that self-assemble in the solid state and can be studied in gaseous and solution phases. Guest loading within pyrogallolarene hexamers in solution has primarily been comprised of solvent molecules with some tertiary amines. A novel solvent-free method for loading guests into the interior of the hexamer has been shown to be effective for encapsulation of a variety of molecules. -
High-Temperature Unimolecular Decomposition Pathways for Thiophene Angayle K
Article pubs.acs.org/JPCA Modeling Oil Shale Pyrolysis: High-Temperature Unimolecular Decomposition Pathways for Thiophene AnGayle K. Vasiliou,*,† Hui Hu,‡ Thomas W. Cowell,† Jared C. Whitman,† Jessica Porterfield,∥,§ and Carol A. Parish‡ † Department of Chemistry and Biochemistry, Middlebury College, Middlebury, Vermont 05753, United States ‡ Department of Chemistry, Gottwald Center for the Sciences, University of Richmond, Richmond, Virginia 23713, United States § Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, United States ABSTRACT: The thermal decomposition mechanism of thiophene has been investigated both experimentally and theoretically. Thermal decomposition experiments were done using a 1 mm × 3 cm pulsed silicon carbide microtubular Δ → reactor, C4H4S+ Products. Unlike previous studies these experiments were able to identify the initial thiophene decomposition products. Thiophene was entrained in either Ar, Ne, or He carrier gas, passed through a heated (300−1700 K) SiC microtubular reactor (roughly ≤100 μs residence time), and exited into a vacuum chamber. The resultant molecular beam was probed by photoionization mass spec- troscopy and IR spectroscopy. The pyrolysis mechanisms of thiophene were also investigated with the CBS-QB3 method using UB3LYP/6-311++G(2d,p) optimized geometries. In particular, these electronic structure methods were used to explore pathways for the formation of elemental sulfur as well as for fi the formation of H2S and 1,3-butadiyne. Thiophene was found to undergo unimolecular decomposition by ve pathways: C4H4S → − − (1) S C CH2 + HCCH, (2) CS + HCCCH3, (3) HCS + HCCCH2, (4) H2S + HCC CCH, and (5) S + HCC CH fi CH2. The experimental and theoretical ndings are in excellent agreement.