Synthesis, Chemistry and Applications of 5-Hydroxymethylfurfural and Its Derivatives
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Synthesis of Terephthalic Acid Via Diels-Alder Reactions with Ethylene and Oxidized Variants of 5-Hydroxymethylfurfural
Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural Joshua J. Pacheco and Mark E. Davis1 Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 Contributed by Mark E. Davis, May 7, 2014 (sent for review April 16, 2014) Terephthalic acid (PTA), a monomer in the synthesis of polyethylene can react to form PX in a one-pot Diels-Alder dehydration re- terephthalate (PET), is obtained by the oxidation of petroleum- action (7). This reaction has received much attention recently, derived p-xylene. There is significant interest in the synthesis of and it is catalyzed by homogeneous Lewis acids and a wide va- renewable, biomass-derived PTA. Here, routes to PTA starting riety of heterogeneous Brønsted acid-containing solids (7–12). from oxidized products of 5-hydroxymethylfurfural (HMF) that can Although nearly 100% PX yields from the Diels-Alder de- be produced from biomass are reported. These routes involve Diels- hydration reaction can be achieved, the reduction step to convert Alder reactions with ethylene and avoid the hydrogenation of HMF HMF to DMF requires expensive metal catalysts and a hydrogen to 2,5-dimethylfuran. Oxidized derivatives of HMF are reacted with source, making this route challenging to commercially imple- ethylene over solid Lewis acid catalysts that do not contain strong ment (13). Therefore, the discovery of routes to PTA from HMF Brønsted acids to synthesize intermediates of PTA and its equally that avoid any hydrogenation steps could be useful. important diester, dimethyl terephthalate (DMT). The partially oxi- An oxidation route to PTA that has previously been consid- dized HMF, 5-(hydroxymethyl)furoic acid (HMFA), is reacted with ered is the Diels-Alder dehydration reaction of ethylene with the high pressure ethylene over a pure-silica molecular sieve containing fully oxidized HMF, 2,5-furandicarboxylic acid (FDCA). -
Report of the Advisory Group to Recommend Priorities for the IARC Monographs During 2020–2024
IARC Monographs on the Identification of Carcinogenic Hazards to Humans Report of the Advisory Group to Recommend Priorities for the IARC Monographs during 2020–2024 Report of the Advisory Group to Recommend Priorities for the IARC Monographs during 2020–2024 CONTENTS Introduction ................................................................................................................................... 1 Acetaldehyde (CAS No. 75-07-0) ................................................................................................. 3 Acrolein (CAS No. 107-02-8) ....................................................................................................... 4 Acrylamide (CAS No. 79-06-1) .................................................................................................... 5 Acrylonitrile (CAS No. 107-13-1) ................................................................................................ 6 Aflatoxins (CAS No. 1402-68-2) .................................................................................................. 8 Air pollutants and underlying mechanisms for breast cancer ....................................................... 9 Airborne gram-negative bacterial endotoxins ............................................................................. 10 Alachlor (chloroacetanilide herbicide) (CAS No. 15972-60-8) .................................................. 10 Aluminium (CAS No. 7429-90-5) .............................................................................................. 11 -
Rigid Biobased Building Blocks: Current Developments and Outlook
Rigid Biobased Building Blocks: Current Developments and Outlook Daan S. van Es Wageningen UR Food &Biobased Research, Wageningen, The Netherlands Received October 15, 2012; Accepted November 12, 2012 ABSTRACT: In this perspectives paper we will look at the state-of-the-art in rigid renewable building blocks for biobased materials, with a focus on two types of carbohydrate-based difunctional monomers, i.e.,isohexides and furan- 2,5-dicarboxylic acid (FDCA). KEYWORDS: Biobased building blocks, FDCA, isohexides, polymers 1 INTRODUCTION (i.e. high purity) aromatic monomers from lignin is not likely in the short term [3]. Whereas in the case of lignin The continuously increasing interest in biomass and the challenges are mostly chemical and technological, biobased materials is fuelled by growing concerns the use of, e.g., terpenes as feedstock for the produc- about fossil feedstock depletion, as well as greenhouse tion of aromatics is severely hampered by the limited gas emissions and global warming. Whereas most of availability compared to the potential demand. Since the current focus is on using terrestrial vegetable bio- carbohydrates (C6 and C5 sugars) are abundantly mass as alternative feedstock for energy carriers (e.g. available they are the most likely candidates as feed- transportation fuels) and chemicals production, aquatic stock for the production of bulk (platform) chemicals biomass (e.g. micro- and macroalgae) is also being for materials production. Basically two approaches can explored as a renewable feedstock source. A success- be distinguished in the transition towards a biobased ful transition from a fossil-feedstock-based economy to (i.e. carbohydrate based) economy; transformation of a biobased economy can only be achieved sustainably biomass feedstocks to existing (fossil based) chemicals, if there is no competition with food and feed produc- also known as drop-in, or transformation of biomass to tion, and negative effects of (indirect) land use change “new” chemicals. -
WO 2017/003293 Al 5 January 2017 (05.01.2017) P O P C T
(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization I International Bureau (10) International Publication Number (43) International Publication Date WO 2017/003293 Al 5 January 2017 (05.01.2017) P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C07D 307/50 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/NL20 16/050469 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, 1 July 20 16 (01 .07.2016) KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, (25) Filing Language: English PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (26) Publication Language: English SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 2015065 1 July 2015 (01.07.2015) NL (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant: FURANIX TECHNOLOGIES B.V. GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, [NL/NL]; 29, Zekeringstraat, 1014 BV Amsterdam (NL). -
A Possible Emergent Cause of Honey Bee Mortality? Lara Zirbes, Bach Kim Nguyen, Dirk C
Subscriber access provided by Université de Liège Review Hydroxymethylfurfural: a possible emergent cause of honey bee mortality? Lara Zirbes, Bach Kim Nguyen, Dirk C. de Graaf, Bruno De Meulenaer, Wim Paul Reybroeck, Eric Haubruge, and Claude Saegerman J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/jf403280n • Publication Date (Web): 15 Oct 2013 Downloaded from http://pubs.acs.org on October 21, 2013 Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts. -
3 in Methyl Levulinate Production from Biomass Carbohydrates
ARTICLE IN PRESS JID: JECHEM [m5G; November 9, 2017;20:14 ] Journal of Energy Chemistry xxx (2017) xxx–xxx Contents lists available at ScienceDirect Journal of Energy Chemistry http://www.journals.elsevier.com/ journal-of-energy-chemistry/ journal homepage: www.elsevier.com/locate/jechem Catalysis performance comparison of a Brønsted acid H 2 SO 4 and a Lewis acid Al 2 (SO 4 ) 3 in methyl levulinate production from biomass carbohydrates ∗ Q1 Xueli Chen, Yuxuan Zhang, Tao Hou, Lujia Han, Weihua Xiao College of Engineering, China Agricultural University, Beijing 10 0 083, China a r t i c l e i n f o a b s t r a c t Article history: An experimental investigation was conducted to understand the roles of the Brønsted acid H 2 SO 4 and Received 5 July 2017 Lewis acid Al (SO ) in methyl levulinate (ML) production from biomass carbohydrates, including glucose, 2 4 3 Revised 5 November 2017 fructose and cellulose. The product distributions with different catalysts revealed that the Lewis acid was Accepted 6 November 2017 responsible for the isomerization of methyl glucoside (MG), producing a significant amount of the subse- Available online xxx quent product 5-methoxymethylfurfural (MMF), while the Brønsted acid facilitated the production of ML Keywords: from MMF. Al 2 (SO 4 ) 3 was efficient for monosaccharide conversion but not for cellulose. Using ball-milled Carbohydrates cellulose with Al 2 (SO 4 ) 3 resulted in a desired ML yield within a reasonable reaction time. The significant Brønsted acid catalysis performances of two types of acids will guide the design of efficient catalytic processes for the Lewis acid selective conversion of biomass into levulinate esters. -
Naming Coordination Compounds
Naming Coordination Compounds Author: Kit Mao Department of Chemistry, Washington University St. Louis, MO 63130 For information or comments on this tutorial, please contact K. Mao at [email protected]. Please click here for a pdf version of this tutorial. A coordination complex is a substance in which a metal atom or ion accepts electrons from (and thus associates with) a group of neutral molecules or anions called ligands. A complex can be an anion, a cation ion, or a neutral molecule. Coordination compounds are neutral substances (i.e. uncharged) in which at least one ion is present as a complex. You will learn more about coordination compounds in the lab lectures for experiment 5 in this course. The coordination compounds are named in the following way. (At the end of this tutorial, there are additional examples that demonstrate how coordination compounds are named.) A. When naming coordination compounds, always name the cation before the anion. This rule holds regardless of whether the complex ion is the cation or the anion. (This is just like naming an ionic compound.) B. In naming the complex ion: 1. Name the ligands first, in alphabetical order, and then name the metal atom or ion. Note: The metal atom or ion is written before the ligands in the chemical formula. 2. The names of some common ligands are listed in Table 1. · Anionic ligands end in “-o.” For anions that end in “-ide”(e.g. chloride, hydroxide), “-ate” (e.g. sulfate, nitrate), and “-ite” (e.g. nirite), change the endings as follows: -ide ® -o; e.g., chloride ® chloro and hydroxide ® hydroxo -ate ® -ato; e.g., sulfate ® sulfato and nitrate ® nitrato -ite ® -ito; e.g., nitrite ® nitrito · For neutral ligands, the common name of the molecule is used (e.g. -
The Effect of Morphology on the Electrochemical Properties of Nanostructured Metal Oxide Thin Films: the Studies Based on Multi
The effect of morphology on the electrochemical properties of nanostructured metal oxide thin films : the studies based on multi-scale time-resolved fast electrogravimetric techniques Fatemeh Razzaghi To cite this version: Fatemeh Razzaghi. The effect of morphology on the electrochemical properties of nanostructured metal oxide thin films : the studies based on multi-scale time-resolved fast electrogravimetric techniques. Chemical Physics [physics.chem-ph]. Université Pierre et Marie Curie - Paris VI, 2016. English. NNT : 2016PA066346. tel-01477408 HAL Id: tel-01477408 https://tel.archives-ouvertes.fr/tel-01477408 Submitted on 27 Feb 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Thèse de doctorat Pour l’obtention du grade de Docteur De l’Université Pierre et Marie Curie École doctorale 388 - Chimie Physique et Chimie Analytique de Paris Centre The Effect of Morphology on the Electrochemical Properties of Nanostructured Metal Oxide Thin Films: The Studies based on Multi-scale Time-resolved Fast Electrogravimetric Techniques Par Fatemeh Razzaghi Directeur de thèse : Dr Hubert Perrot Présentée et soutenue publiquement le 29 septembre 2016, Devant un jury composé de : Nicole Jaffrezic DR CNRS Émérite Rapporteur Francois Tran-Van Prof. -
Dehydration of D-Fructose to 5-Hydroxymethyl-2-Furfural in DMSO
www.nature.com/scientificreports OPEN Dehydration of d‑fructose to 5‑hydroxymethyl‑2‑furfural in DMSO using a hydrophilic sulfonated silica catalyst in a process promoted by microwave irradiation Sandro L. Barbosa1*, Milton de S. Freitas1, Wallans T. P. dos Santos1, David Lee Nelson1, Stanlei I. Klein2, Giuliano Cesar Clososki3, Franco J. Caires3, Adriano C. M. Baroni4 & Alexandre P. Wentz5 2 3 −1 + SiO2‑SO3H, with a surface area of 115 m /g, pore volumes of 0.38 cm g and 1.32 mmol H /g, was used as a 10% w/w catalyst for the preparation of 5‑hydroxymethyl‑2‑furfural (HMF) from fructose. A conversion of 100% was achieved in a microwave reactor during 10 min at 150 °C in DMSO, with 100% selectivity for HMF, at a molar ratio of fructose: DMSO equal to 1:56. The catalyst could be re‑used three times. 5-Hydroxymethyl-2-furfural (HMF), which can be obtained from the dehydration of sugars, has a high potential as renewable raw material for the production of a variety of important molecules containing or derived of the furan ring, including biofuels, solvents, drugs, and biopolymer monomers 1–3. Tus, several studies have described the synthesis of HMF by catalytic dehydration of fructose4–18, Fig. 1. Glucose is less efcient than fructose for the synthesis of HMF19–21; according to Kuster22,23 and Zakrzewska et al.24, this results from the diference in stability of the two cyclical sugar structures, which are composed of six atoms in glucose (pyranose form) and fve atoms in fructose (furanose form). -
Supplementary Information Experimental Products (Furfurals) Were Calculated by Comparison with an Internal Standard Solvent As the Reference Sample (N-Octanol)
Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2019 Supplementary Information Experimental products (furfurals) were calculated by comparison with an internal standard solvent as the reference sample (n-octanol). Chemicals The MLA and n-octanol relevant line equation is For this study, bamboo particles was collected from a local y=2.06543x–0.02107 (coefficient of correlation R2 =0.9998), farm in Jiangsu Province, China. All materials were passed the intermediate products (such as MMF) and n-octanol through a 250–425 μm sieve and dried to a constant weight for relevant line equation is y=1.9657x+0.0612 (coefficient of 24 h at 105 °C. The absolute-dried particles were kept in a correlation R2 = 0.9996). desiccator until used. The High Performance Liquid Chromatography HPLC instrument (Shimadzu LC–10ATVP, Aminex HPX–87H column) Analytic methods with a RID-20A detector was used to quantitative analyzed the Gas chromatography (GC) mass spectrometry (MS) (Agilent methyl pentose glycosides (C5-Gly) and methyl hexose 5975C VL MSD) analysis was used a HP-5 fused capillary glucosides (C6-Gly). Used 0.005 mmol sulfuric acid (sonication, column (l= 30 m, i d= 0.32 mm, t= 0.25 μm) with poly dimethyl deaeration) in water as the mobile phase and the flow rate siloxane with 5% phenyl methyl substitution as the stationary was of 0.5 mL/min, and the column temperature was kept at phase. The injection mode was split at a rate of 35. The carrier 45 °C for 30 min. The standard curve of concentration of −1 gas was He at a flow rate of 1.5 mL min . -
Microwave Assisted Synthesis of Dehydrated Sugar Derivatives Hydroxymethylfurfural, Levulinic Acid, Anhydrosugar Alcohols, and E
(19) TZZ _T (11) EP 2 598 466 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 51/00 (2006.01) C07D 307/02 (2006.01) 28.09.2016 Bulletin 2016/39 C07C 67/00 (2006.01) C07D 307/93 (2006.01) C07D 493/04 (2006.01) C07D 307/46 (2006.01) (2006.01) (2006.01) (21) Application number: 11812946.9 C07D 307/48 C07D 307/50 C07C 59/185 (2006.01) (22) Date of filing: 18.07.2011 (86) International application number: PCT/US2011/044324 (87) International publication number: WO 2012/015616 (02.02.2012 Gazette 2012/05) (54) MICROWAVE ASSISTED SYNTHESIS OF DEHYDRATED SUGAR DERIVATIVES HYDROXYMETHYLFURFURAL, LEVULINICACID, ANHYDROSUGAR ALCOHOLS, AND ETHERS THEREOF MIKROWELLENUNTERSTÜTZTE SYNTHESE VON DEHYDRIERTEN ZUCKERDERIVATEN, HYDROXYMETHYLFURFURAL, LÄVULINSÄURE, ANHYDROZUCKERALKOHOLEN SOWIE DEREN ETHERN SYNTHÈSE ASSISTÉE PAR RAYONNEMENT MICROONDES DES DÉRIVÉS DE SUCRES DÉSHYDRATÉS HYDROXYMÉTHYLFURFURAL, ACIDE LÉVULINIQUE, ALCOOLS DE SUCRE ANHYDRES ET LEURS ÉTHERS (84) Designated Contracting States: (74) Representative: dompatent von Kreisler Selting AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Werner - GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Partnerschaft von Patent- und Rechtsanwälten PL PT RO RS SE SI SK SM TR mbB Deichmannhaus am Dom (30) Priority: 30.07.2010 US 369350 P Bahnhofsvorplatz 1 50667 Köln (DE) (43) Date of publication of application: 05.06.2013 Bulletin 2013/23 (56) References cited: WO-A2-2009/155020 US-A- 5 558 899 (73) Proprietor: Archer-Daniels-Midland Company US-A1- 2007 213 544 US-A1- 2007 213 544 Decatur, IL 62526 (US) US-A1- 2009 156 841 US-A1- 2009 156 841 US-A1- 2009 253 920 US-A1- 2009 281 338 (72) Inventors: • HOWARD, Stephen J. -
Thulhu Muttur
THULHUUS009793542B2 MUTTUR (12 ) United States Patent ( 10 ) Patent No. : US 9 , 793 ,542 B2 Nelson et al. ( 45 ) Date of Patent: Oct . 17 , 2017 (54 ) BETA - DELITHIATED LAYERED NICKEL (58 ) Field of Classification Search OXIDE ELECTROCHEMICALLY ACTIVE CPC .. .. HO1M 4 /244 ; HOTM 4 / 366 ; HOTM 4 /52 ; CATHODE MATERIAL AND A BATTERY HOTM 4 / 131; HOTM 4 / 32 ; HO1M 4 / 525 INCLUDING SAID MATERIAL See application file for complete search history . ( 71 ) Applicant : DURACELL U . S . OPERATIONS, ( 56 ) References Cited ??? INC ., Wilmington , DE (US ) U . S . PATENT DOCUMENTS (72 ) Inventors : Jennifer Anne Nelson , Waltham , CT 2 , 956 , 860 A 10 / 1960 Welsh et al . ( US ) ; David Lloyd Anglin , Brookfield , 3 ,437 ,435 A 4 /1969 Moore et al . CT (US ) ; Mariarosa Brundu , Budduso (Continued ) (IT ) ; Paul Albert Christian , Norton , MA (US ) FOREIGN PATENT DOCUMENTS ( 73 ) Assignee : DURACELL U . S . OPERATIONS , 1263697 12 / 1989 INC . , Wilmington , DE (US ) 0 702 421 A1 3 / 1996 (Continued ) ( * ) Notice : Subject to any disclaimer, the term of this ???????? patent is extended or adjusted under 35 OTHER PUBLICATIONS U . S . C . 154 ( b ) by 213 days. PCT International Search Report with Written Opinion in corre ( 21) Appl. No .: 14 /625 ,876 sponding Int' l appln . PCT/ US2015 /021381 dated Aug . 11 , 2015 . ( 22 ) Filed : Feb . 19 , 2015 (Continued ) Primary Examiner — Stewart Fraser (65 ) Prior Publication Data Assistant Examiner — Rachel L Zhang (74 ) Attorney , Agent, or Firm — Marshall , Gerstein & US 2015 /0280234 A1 Oct . 1 , 2015 Borun LLP Related U . S . Application Data (57 ) ABSTRACT The invention is directed towards an electrochemically (60 ) Provisional application No . 61 / 971, 667 , filed on Mar.