Dissertations / Theses on the topic 'Allylic alcohols'
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Brennan, Meabh B. "Chemo- and stereoselective oxidation of allylic amino alcohols." Thesis, University of Oxford, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.531953.
Full textHackett, Simon F. J. "Selective Oxidation of Allylic Alcohols on Palladium Catalysts." Thesis, University of York, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.490272.
Full textGao, Y. (Yun). "Synthesis and synthetic transformations of allylic alcohols, epoxy alcohols, and 1,2-cyclic sulfates." Thesis, Massachusetts Institute of Technology, 1988. http://hdl.handle.net/1721.1/14588.
Full textKhan, Afzal. "Synthesis and reactions of epoxides." Thesis, University of Sheffield, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.286509.
Full textPeters, Byron. "Iridium Catalysed Asymmetric Hydrogenation of Olefins and Isomerisation of Allylic Alcohols." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-122419.
Full textAt the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.
Smith, Torben J. N. "Enantioselective deprotonations of three membered rings." Thesis, University of Nottingham, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.243768.
Full textLee, Wai-Man. "Stereocontrolled synthesis of polysubstituted tetrahydropyrans and #delta#-lactones via tandem [2,3]-Wittig-anionic oxy-Cope rearrangement." Thesis, University of Liverpool, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.243034.
Full textEvans, Paul. "The epoxy Ramberg Bäcklund rearrangement (ERBR) and related studies." Thesis, University of York, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.265373.
Full textOtoo, Barnabas. "Conjugate Additions and Transposition of the Allylic Alcohols of Enol Ethers of 1, 2-Cyclohexanedione." Digital Commons @ East Tennessee State University, 2010. https://dc.etsu.edu/etd/1748.
Full textQiu, Shuai. "Trifluoromethoxylation of Allylic Alcohols via 1,2-Aryl Migration Promoted by Visible Light-Mediated Photoredox Catalysis." Thesis, KTH, Skolan för kemi, bioteknologi och hälsa (CBH), 2020. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-278836.
Full textFotoredoxkatalys via ljus inom det synliga spektrat har visat sig vara ett kraftfullt verktyg för att gynna reaktioner inom organisk syntes. Detta projekt genomfördes med syfte att utveckla verktyg avsedda för att förutspå reaktivitetsmönster vid fotoredoxkatalys med synligt ljus. Fluorinering och trifluorometoxylering är viktiga verktyg inom organisk syntes. Fluorineringsreaktionen har studerats länge och har kunnat genomföras under milda reaktionsbetingelser, medan generering av trifluorometoxyradikal vid rumstemperatur och atomsfärstryck fortfarande är en utmaning. Reaktionen i det här projektet är designad för att kringgå instabilitetsproblemet och ta kontroll över katalysmomentet, under fotokatalysförhållanden i synligt ljus. Reaktionen utfördes i rumstemperatur med en reaktionstid på 60 minuter, med acetonitril som lösningsmedel och blå LED (10 W) som extern ljuskälla. Inget av substraten reagerade till den önskade produkten. Mer överraskande var att 3,3-difenylprop-2-en-1-ol erhölls som sidoprodukt vid alla reaktionsstillfällen. Samma sidoprodukt upptäcktes även vid reaktion genomförd i dagsljus, vilket indikerar att reaktionen skedde utan någon extern ljuskälla. Således skedde ingen fotoredoxkatalys.
Love, Christopher J. "The carbometallation of allylic alcohols : scope stereochemistry, and a synthesis of a precursor to Tsukubaenolide (FK 506)." Thesis, University of Southampton, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.303109.
Full textLiu, Jianguo. "Iridium Catalysed Asymmetric Hydrogenation of Olefins and Dynamic Kinetic Resolution in the Asymmetric Hydrogenation of Allylic Alcohols." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2017. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-140923.
Full textAt the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 5: Manuscript.
Dai, Xiaoyang. "Hydride transfer reactions of trifluoromethylated allylic alcohols and ketimines & nucleophilic trifluoromethylthiolation of Morita-Baylis-Hillman Carbonates." Thesis, Rouen, INSA, 2014. http://www.theses.fr/2014ISAM0018/document.
Full textWe have developed new accesses for the construction of molecules featuring Csp3-CF3 and Csp3-SCF3 motifs. Two atom-economical hydride transfer reactions of trifluoromethylated compounds by transition-metal catalysis were realized: 1) the isomerization of trifluoromethylated allylic alcohols by iron (II) complexes; 2) the enantioselective transfer hydrogenation of trifluoromethylated ketimines by a chiral complex of ruthenium and isopropanol as hydride source for the preparation of optically pure trifluoromethylated amines in high yields and high enantioselectivities. The nucleophilic allylic trifluoromethylthiolation of Morita-Baylis-Hillman derivatives was investigated. The regio- and stereoselective access to thermodynamic trifluoromethylthiolated products has been achieved by combination of S8/KFfMe3SiCF3/DMF in good yields. The kinetic trifluoromethylthiolated products were obtained by using Zard's trifluoromethylthiolating reagent
Thalén, Lisa K. "Transition metal- and enzyme-catalyzed reactions of primary amines and allylic alcohols : powerful tools in the preparation of pharmaceutically important compounds /." Stockholm : Department of Organic Chemistry, Stockholm University, 2010. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-38839.
Full textAt the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript. Paper 7: Manuscript. Härtill 7 uppsatser.
Gadamsetty, Surendra Babu. "Application of sulfonimidoyl substituted allyltitanium (IV) complexes to the asymmetric synthesis of alkenyloxiranes, 2,3-dihydrofurans, tetrahydrofurans, unsaturated proline analogues and allylic alcohols." [S.l.] : [s.n.], 2007. http://deposit.ddb.de/cgi-bin/dokserv?idn=983701350.
Full text祐士, 中村, and Yushi Nakamura. "原子効率に優れたアリルアルコール類の新規触媒的分子変換法に関する研究." Thesis, https://doors.doshisha.ac.jp/opac/opac_link/bibid/BB13045024/?lang=0, 2017. https://doors.doshisha.ac.jp/opac/opac_link/bibid/BB13045024/?lang=0.
Full textDevelopment of novel transform methods of allylic alcohols catalyzed by transition metal complexes was studied. In the result, development of anti-Markovnikov hydroamination and hydroalkoxylation of allylic alcohols catalyzed by uniquely prepared ruthenium catalysts, which had a advanced transfer hydrogen ability, on the basis of a character as a alcohol of allylic alcohols and "Borrowing hydrogen" methodology was achieved at 100% atom economy.
博士(工学)
Doctor of Philosophy in Engineering
同志社大学
Doshisha University
Bunge, Alexander. "Geminale Dihydroperoxide als Sauerstofftransferreagenzien und Synthesebausteine." Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I, 2011. http://dx.doi.org/10.18452/16436.
Full textIn the course of this dissertation thesis the preparation and reactions of geminal dihydroperoxides were researched. The hereby synthesized dihydroperoxides were used as an oxygen transfer reagent, especially for enantioselective epoxidation, as well as a building block for the synthesis of 1,2,4,5-tetroxanes. A method for synthesis of gem-dihydroperoxides that was found in our workgroup was first optimized concerning reaction conditions, and later utilized to synthesize a large number of dihydroperoxides. It was notably possible to synthesize primary DHPs from aliphatic aldehydes for the first time. Also for the first time, a large number of enantiomerically pure gem-DHP was prepared by this method. Additional enantiomerically pure DHPs were made by ozonolysis of olefinic terpenes using ethereal hydrogen peroxide solution. The enenantiomerically pure DHPs were utilized to both epoxidize 2-substituted naphthoquinones as well as allylic alcohols, especially tertiary allylic alcohols. The latter kind does not react via the normally used Sharpless epoxidation. Additionally, enantioenriched sulfoxides could be prepared from sulfides. This is the first time that geminal dihydroperoxides were used for enantioselective oxygen transfer. Primary aliphatic DHPs were further utilized to prepare previously unknown 1,2,4,5-tetroxanes. Notably it was found that condensation with orthoesters reliably yielded alkoxy-substiuted tetroxanes. These were only described in a very few cases in literature before.
Gerez, Thierry. "Développement de catalyseurs pour le transfert d'hydrogène : application à des molécules biosourcées." Thesis, Lyon 1, 2014. http://www.theses.fr/2014LYO10246/document.
Full textIn this study, we evaluated the compatibility of polyfunctional alcohols with catalytic aerobic oxidation systems. Geraniol dehydrogenation was carried out in mild conditions (t-BuOH / water mixture as solvent, 40°C) in the presence of Pt / C (promoted with Bi to avoid leaching). These catalysts are efficients for the oxidation of 8-Chloro-1-Octanol into corresponding acid at 90°C. However, other reactants were not selectively transformed into aldehyds or acids because of their oxygen sensivity (alcool-A) or their particular reactivity toward cyclization products (5-Chloro-1-Pentanol). In parallel, H transfer dehydrogenation was developed in anaerobic conditions. Geraniol was choosen as a model molecule since it can be selectively dehydrogenated or isomerizd (a reducible function on the substrate is hydrogenated when alcohol function is dehydrogenated). Some noble metals were evaluated for these reactions (Pd in the presence of alkene as H acceptor or Ag for acceptorless dehydrogenation), but performances and selectivities are quite low. Copper catalysts showed better results, and a lot of supports were evaluated. Selectivity toward dehydrogenation product (citral) is not total when styrene is used as hydrogen acceptor, but the use of another H acceptor (confidential) in the presence of copper supported on modified hydrotalcite catalyst allows selective dehydrogenation of geraniol without isomerization intro citronellal. Without H acceptor, this catalyst leads to selective isomerization of secondary allylic alcohols into saturated ketones (90 % selectivity)
Kasprzyk, Milena, and milena kasprzyk@freehills com. "Synthetic Studies Towards the Tridachione Family of Marine Natural Products." Flinders University. Chemistry, Physics and Earth Sciences, 2008. http://catalogue.flinders.edu.au./local/adt/public/adt-SFU20081107.085933.
Full textSchäfer, Christian. "Reactivity of acetylenic ω-keto-esters towards transition metal complexes : synthesis of polycyclic motives of natural products." Thesis, Strasbourg, 2013. http://www.theses.fr/2013STRAF006/document.
Full textIn this work, the reactivity of acetylenic ω-ketoesters towards different metal complexes was investigated. When acetylenic ω-ketoesters are submitted to Ti(OiPr)4/iPrMgBr, the formation of fused bicyclic γ-hydroxy-α,β-unsaturated esters was observed. The products were obtained with absolute selectivity in regard to the ring junction formed (cis) and the configuration of the double bond (E) and could be transformed into the corresponding α,β-unsaturated lactones, substructures of various natural products. When ω-ketoalkynes are used in Ag(I)-catalyzed cycloisomerization reactions, the formation of spirocyclic compounds was observed. By taking advantage of the reaction intermediates of this reaction, it was possible to isolate the corresponding spirocyclic alkenyl iodides. Performing cycloisomerization reactions with acetylenic ω-ketoesters, spirocyclic α,β-unsaturated esters are formed. We could show that these products are valuable substrates for the formation of 6-5-5- and 6-6-5-fused tricyclic systems which represent the skeleton of a large group of natural products
Black, Phillip James. "Catalytic electronic activation : the addition of nucleophiles to an allylic alcohol." Thesis, University of Bath, 2002. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.275782.
Full textFordred, Paul. "Synthetically useful alkene isomerisation and hydroboration reactions." Thesis, University of Bath, 2012. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.558880.
Full textMorrison, Ryan John. "Development and Application of Methods for Enantioselective Synthesis of Amines and Alcohols:." Thesis, Boston College, 2020. http://hdl.handle.net/2345/bc-ir:108988.
Full textHomoallylic amines and alcohols, particularly those amenable to further functionalization, are among the most widely used building blocks in chemical synthesis and are typically accessed by addition of an allyl-metal compound to an electrophile. Studies discussed herein have focused on advancing stereoselective synthesis of versatile allylboron compounds and their utilization in catalytic regio-, diastereo-, and enantioselective addition to various electrophiles. Mechanistic principles have been central to the investigations described in this thesis, and it has been on this basis that catalytic strategies for practical synthesis of bioactive molecules were developed. Chapter One. Vicinal amino alcohols are ubiquitous in natural products and serve as versatile synthetic intermediates and we envisaged that diastereo- and enantioselective additions of O-substituted allyl boronates offers an attractive option to access these motifs. In the presence of zinc (II) methoxide as co-catalyst, it will be demonstrated that sequence of events may occur, wherein isomerization of an initially formed allyl complex occurs prior to addition of an aldimine with kinetic selectivity. As will be described, through the use of an optimal catalyst, N-protecting/activating group and appropriate reaction conditions, differentially protected vicinal amino alcohol derivatives may be synthesized in high enantiopurity. The utility of the approach is highlighted through synthesis of an NK1 agonist. Chapter Two. It will be demonstrated that additions of various organoboron compounds converts readily accessible and easy-to-handle silyl-substituted -tertiary amines. Contrary to additions to aldimines, isomerization of the initially generated aminophenol-allyl complex is preempted, suchthat linear products are favored. DFT analysis suggests that high enantioselectivity likely originates from attractive electrostatic interaction between a trifluoromethyl group and the catalyst’s ammonium moiety. The synthetic utility was highlighted through concise, enantioselective synthesis of a key intermediate of a recently reported BACE-1 inhibitor on gram scale. Chapter Three. This section details the development of a method for direct synthesis of homoallylic alcohols bearing a Z-alkenyl chloride, which may be directly subjected to stereo-retentive cross coupling without wasteful protection/deprotection or redox operations. Products were obtained in high regio- and enantioselectivity for aliphatic, alkenyl- and heteroaryl-substituted aldehydes. The approach was utilized in a concise, protecting group-free synthesis of anti-tumor agent mycothiazole. Chapter Four. A method for stereoselective synthesis of fluorine-containing trisubstituted allyl boronates will be presented. It will then be illustrated that in the presence of an appropriate aminophenol catalyst, a large assortment of homoallylic alcohols containing a quaternary fluoro- and trifluoromethyl-substituted stereogenic center may be obtained with efficiency and high diastereo- and enantioselectivity. The obtained products were then elaborated to the furanose core of Sofosbuvir, a recently approved treatment for hepatitis C
Thesis (PhD) — Boston College, 2020
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
El, Karroumi Jamal. "Réactions de carbonylation de substrats naturels de plantes." Thesis, Toulouse, INPT, 2014. http://www.theses.fr/2014INPT0033/document.
Full textThe catalytic functionnalisation of the natural substrates have been developped to increase their own biological activity or to give them new biological properties. The reactions such as hydroformylation, alkoxycarbonylation and cyclocarbonylation in presence of carbon monoxide catalyzed by rhodium or palladium complexes or cycloisomerisation catalyzed by gold or platinium complexes give an access to new interesting molecules with high selectivity. In first part we have been interested in study of the essential oil of the Atlas Cedar (Cedrus Atlantica). We focused in this study on the oxygenated fraction, which contains the two sesquiterpenic ketone,isomers Z- and E-α-atlantone. Starting from allylic alcohols derived from α-atlantone, the cyclocarbonylation reaction catalyzed by palladium complexes have been investigated. This reaction provide a mixture of five and six membered ring lactones with excellent conversion and excellent chemioselectivity. Different catalytic systems [PdCl2L2]/SnCl2.2H2O or [Pd(OAc)2]/L have been studied. The regiochemical control depends on the nature of the ligand L. The monophosphine ligands favor the formation of the six-membered ring lactones obtained as two diastereomers, while the diphosphine ligands allow the formation of the five- membered ring lactone obtained as four diastereomers. These new lactones were fully characterized by 1D and 2D NMR and mass spectrometry. Monocrystals of the six- and five-membered ring lactones suitable for X-ray diffraction analysis have been obtained. In a second part the hydroformylation reaction of estragol, a natural allylbenzene extracted from the essential oil of estragon, have been studied with the catalytic system [Rh(cod)(OMe)]2/phospholes. All the phosphole ligands show good activities and chemoselectivities in the hydroformylation of estragol and affords the linear aldehyde corresponding as a major product. In a preliminary study, we have investigated the cycloisomerisation reaction of o-tethered enynes derived from α-atlantones catalyzed by gold or platinum complexes
Al, Badri Hashim. "Synthèse et réactivité d'énamines phosphoniques fonctionnelles et de phosphonates allyliques. Applications à la synthèse de diènes fonctionnels utilisés dans la réaction de Diels-Alder." Rouen, 1996. http://www.theses.fr/1996ROUES054.
Full textLee, Darren Frank. "The catalysed reactions of allyl alcohol using the microporous materials zeolite Y and TS-1." Thesis, University of Liverpool, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.386828.
Full textBoogaerts, Ine Ida Françoise. "Novel catalysts for the hydroxymethylation of allyl alcohol : a convenient synthetic route to 1, 4-butanediol." Thesis, University of St Andrews, 2009. http://hdl.handle.net/10023/959.
Full textBatt, Frédéric. "Approches synthétiques vers le mycothiazole-4,19-diol : utilisation du palladium en synthèse organique." Phd thesis, Université Claude Bernard - Lyon I, 2009. http://tel.archives-ouvertes.fr/tel-00654585.
Full textKan, Tze-wai Jovi, and 簡紫慧. "Development of new polymer-supported reagents for organic synthesis, solvent effects in samarium promoted allylic alcohol cyclopropanationreactions and time resolved resonance studies of the photodeprotectionof p-hydroxyphenacyl caged phototrigger compounds." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2006. http://hub.hku.hk/bib/B37925660.
Full textKan, Tze-wai Jovi. "Development of new polymer-supported reagents for organic synthesis, solvent effects in samarium promoted allylic alcohol cyclopropanation reactions and time resolved resonance studies of the photodeprotection of p-hydroxyphenacyl caged phototrigger compounds." Click to view the E-thesis via HKUTO, 2006. http://sunzi.lib.hku.hk/hkuto/record/B37925660.
Full textRahm, Fredrik. "Chiral Pyridine-Containing Ligands for Asymmetric Catalysis. Synthesis and Applications." Doctoral thesis, KTH, Chemistry, 2003. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3564.
Full textThis thesis deals with the design and syntheses of chiral,enantiopure pyridinecontaining ligands and their applicationsin asymmetric catalyis.
Chiral pyridyl pyrrolidine ligands and pyridyl oxazolineligands were synthesized and employed in thepalladium-catalysed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. Theinfluence of the steric properties of the ligands wereinvestigated.
Ditopic ligands, containing crown ether units as structuralelements, were synthesized and some of the ligands were used asligands in the palladiumcatalysed allylic alkylation of1,3-diphenyl-2-propenyl acetate with dimethyl malonate. A smallrate enhancement was observed, compared with analogous ligandslacking the crown ether unit, when these ditopic ligands wereused in dilute systems.
A modular approach was used to synthesize chiralenantiomerically pure pyridyl alcohols and C2-symmetric2,2-bipyridines, with the chirality originating from thechiral pool. Electronic and steric properties of the compoundswere varied and they were used as ligands in theenantioselective addition of diethylzinc to benzaldehyde. Thesense of asymmetric induction was found to be determined by theabsolute configuration of the carbinol carbon atom. Theelectronic properties of the ligands had a minor influence onthe levels of enantioselectivity induced by the ligands.
Chiral pyridyl phosphinite ligands and pyridyl phosphiteligands were synthesized from the pyridyl alcohols andevaluated as ligands in palladiumcatalysed allylic alkylations.With the phosphinite ligands, the sense of chiral induction wasfound to be determined by the absolute configuration of theformer carbinol carbon atom. A kinetic resolution of theracemic starting material was observed with one of thephosphite ligands. Moderate enantioselectivities wereachieved.
Kewords:asymmetric catalysis, chiral ligand, chiralpool, oxazoline, crownether, ditopic receptor, bipyridine,pyridyl alcohol, modular approach, P,Nligand, diethylzinc,allylic alkylation.
Lemar, Katey M. "Cell death in the human pathogen Candida albicans : effects of garlic (Allium sativum), and garlic constituents allyl alcohol and diallyl disulphide." Thesis, Cardiff University, 2005. http://orca.cf.ac.uk/54550/.
Full textGayet, Arnaud. "Development of New Chiral Bicyclic Ligands : Applications in Catalytic Asymmetric Transfer Hydrogenation, Epoxidations, and Epoxide Rearrangements." Doctoral thesis, Uppsala University, Organic Chemistry, 2005. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-4753.
Full textThis thesis describes the synthesis and application of new chiral bicyclic ligands and their application in asymmetric catalysis. The studies involved: [i] The development of novel chiral bicyclic amino sulfur ligands and their use in transfer hydrogenation. [ii] The development of the kinetic resolution of racemic epoxide through the use of chiral lithium amides. [iii] The synthesis and application of chiral bicyclic amine in the organocatalysed epoxidation of alkenes. [iv] Development and application of new chiral diamine ligands in the rearrangement of epoxides into allylic alcohols.
[i] The preparation of two-series of amino thiol ligands based on the structure of camphor is described, together with their application in the iridium-catalysed asymmetric transfer hydrogenation of acetophenone using isopropanol as the hydrogen source. Excellent activity and good enantioselectivity have been achieved using 2 mol% of chiral ligand in combination with [IrCl(COD)]2.
[ii] The chiral diamines (1S,3R,4R)-3-(pyrrolidine-1-ylmethyl)-2-aza-bicyclo[2.2.1]heptane and its (2R,5R)-dimethylpyrrolidine derivative were applied to the kinetic resolution of a variety of racemic 5-7 membered cycloalkene oxides with lithium diisopropylamide (LDA) as the bulk base. Using 5 mol% of the chiral diamines, both unreacted epoxides and allylic alcohols could be produced in enantiomeric excess up to 99%.
[iii] The synthesis of chiral bicyclic amines and their use in the organocatalysed epoxidation of alkene has been described. Using a substoichiometric amount of the chiral amines and aldehydes as ligands precursors, with Oxone® as oxidant, a good activity but moderate enantioselectivity was observed for the epoxidation of trans-stilbene.
[iv] The preparation of 6-substituted-7-bromo-aza-bicyclo[2.2.1]heptanes via nucleophilic addition of organocopper reagents to 3-bromo-1-azoniatricyclo[2.2.1.0]heptyle bromide has been described. These compounds have been utilised as chiral building blocks in the preparation of novel chiral diamine ligands, which have been successfully applied to the catalysed asymmetric rearrangement of epoxide into the corresponding allylic alcohol.
Guigné, Claire de. "Réactions d'éthers de diénol pour l'accès à des structures terpéniques : condensation carbocationique et métallation vinylique." Rouen, 1997. http://www.theses.fr/1997ROUES034.
Full textBresciani, Stefano. "Stereospecific dehydroxyfluorination and the synthesis of trifluoro D-hexose sugar analogues." Thesis, University of St Andrews, 2011. http://hdl.handle.net/10023/1878.
Full textLima, Luis Ferreira de. "Obten??o de ?lcool al?lico (PROP-2-EN-1-OL) a partir da glicerina derivada do biodiesel de ?leo de mamona." Universidade Federal do Rio Grande do Norte, 2012. http://repositorio.ufrn.br:8080/jspui/handle/123456789/13016.
Full textCoordena??o de Aperfei?oamento de Pessoal de N?vel Superior
In this work, biodiesel was produced from castor oil that was a byproduct glycerin. The molar ratio between oil and alcohol, as well as the use of (KOH) catalyst to provide the chemical reaction is based on literature. The best results were obtained using 1 mol of castor oil (260g) to 3 moles of methyl alcohol (138g), using 1.0% KOH as catalyst at a temperature of 260 ? C and shaken at 120 rpm. The oil used was commercially available, the process involves the reaction of transesterification of a vegetable oil with methyl alcohol. The product of this reaction is an ester, biodiesel being the main product and the glycerin by-product which has undergone treatment for use as raw material for the production of allyl alcohol. The great advantage of the use of glycerin to obtain allyl alcohol is that its use eliminates the large amount of waste of the biodiesel and various forms of insult to the environment. The reactions for the formation of allyl alcohol was conducted from formic acid and glycerin in a ratio 1/1, at a temperature of 260oC in a heater blanket, being sprayed by a spiral condenser for a period of 2 hours and the product obtained contains mostly the allylic alcohol .. The monitoring of reactions was performed by UV-Visible Spectrophotometer: FTIR Fourier transform, the analysis showed that these changes occur spectrometer indicating the formation of the product allylic alcohol (prop-2-en-1-ol) in the presence of water, This alcohol was appointed Alcohol GL. The absorption bands confirms that the reaction was observed in (? C = C) 1470 -1600 cm -1 and (? CO), 3610-3670 attributed to C = C groups and OH respectively. The thermal analysis was carried out in a thermogravimetric analyzer SDT Q600, where the mass and temperature are displayed against time, that allows checking the approximate rate of heating. The innovative methodology developed in the laboratory (LABTAM, UFRN), was able to treat the glycerine produced by transesterification of castor oil and used as raw material for production of allyl alcohol, with a yield of 80%, of alcohol, the same is of great importance in the manufacture of polymers, pharmaceuticals, organic compounds, herbicides, pesticides and other chemicals
Neste trabalho o biodiesel foi produzido a partir de ?leo de mamona que teve como subproduto a glicerina. A raz?o molar entre ?leo e ?lcool, bem como o uso do (KOH) como catalisador qu?mico para proporcionar a rea??o, foi baseada em dados da literatura. Os melhores resultados foram obtidos, utilizando 1 mol de ?leo de mamona (260g) para 3 mols de ?lcool met?lico (138g). O ?leo utilizado foi adquirido comercialmente, o processo de transesterifica??o envolve a rea??o do ?leo vegetal com um ?lcool met?lico. O produto dessa rea??o ? um ?ster, sendo o biodiesel o seu principal produto e a glicerina o sub-produto a qual foi submetida a tratamento para uso como mat?ria-prima para a obten??o do ?lcool al?lico. A grande vantagem do uso da glicerina para obten??o de ?lcool al?lico ? que sua utiliza??o elimina a grande quantidade de res?duos do biodiesel e v?rias formas de agress?o ao meio ambiente. As rea??es para forma??o do ?lcool alilico foram conduzidas a partir de ?cido f?rmico e glicerina, em uma raz?o 1/1, sob temperatura de 260oC, em uma manta aquecedora, sendo vaporizado por um condensador em espiral por um per?odo de 2 horas, e o produto obtido contem em sua grande maioria o ?lcool al?lico. O acompanhamento das rea??es foi realizado por Espectrofot?metro UV-Vis?vel: FTIR com transformada de Fourier, a an?lise revelou que estas altera??es espectrom?tricas ocorrem indicando a forma??o do produto ?lcool al?lico (prop-2-en-1-ol), em presen?a de ?gua, este ?lcool foi nomeado de ?lcool GL. As bandas de absor??o que confirmam a rea??o foram observadas em (? C=C) em 1470 -1600 cm-1 e em (? C-O), 3610 3670 atribu?das aos grupos C=C e O-H respectivamente. A analise t?rmica foi realizada em um analisador Termogravim?trico SDT Q600, onde a massa e a temperatura ser?o exibidos em fun??o do tempo, isto permite a verifica??o aproximada da taxa de aquecimento. A metodologia inovadora desenvolvida no laborat?rio (LABTAM, UFRN), foi capaz de tratar a glicerina produzida, atrav?s da transesterifica??o de ?leo de mamona e utilizar como mat?ria prima para produ??o do ?lcool al?lico, apresentando um rendimento de 80%, deste ?lcool, o mesmo ? de grande import?ncia na fabrica??o de pol?meros, medicamentos, compostos org?nicos, herbicidas, pesticidas e outros produtos qu?micos
Santos, Regina Claudia Rodrigues dos. "Catalisadores BimetÃlicos de Ãxidos de MoâCu (Ni ou Co) Suportado em Alumina para ConversÃo do Glicerol a IntermediÃrios QuÃmicos." Universidade Federal do CearÃ, 2016. http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=16858.
Full textA viabilidade econÃmica da produÃÃo do biodiesel depende do uso do glicerol, subproduto com estrutura multifuncional, considerado matÃriaâprima bio-renovÃvel, de grande potencial para ser transformado a combustÃveis ou produtos quÃmicos de maior valor agregado. Com o intuito de contribuir para o desenvolvimento dessa linha de pesquisa, foi realizado estudo do potencial catalÃtico da γ-Al2O3 modificada com Ãxido de molibdÃnio e promotores (Cu, Ni ou Co), na reaÃÃo de desidrataÃÃo do glicerol a intermediÃrios quÃmicos com aplicaÃÃo industrial. A estratÃgia foi sintetizar esferas de Al2O3 por mÃtodo hÃbrido, as quais apresentam interessantes propriedades estruturais, texturais e quÃmicas para em seguida impregnar com precursores dos metais via mÃtodo nÃo-convencional (Pechini). A composiÃÃo dos materiais foi escolhida com o objetivo de avaliar o efeito bifuncional causado pela combinaÃÃo das propriedades Ãcido/bÃsicas e redox de catalisadores de molibdÃnio suportado em alumina. Para fins comparativos foi testado catalisador comercial Ni-Mo/Al2O3 com elevada acidez e porosidade. Os catalisadores foram caracterizados por: ICP-OES, FRX, TGA/DTA, DRX, MEV, IV, TPR-H2, TPD-CO2, isotermas de adsorÃÃo/dessorÃÃo de N2, e acidez atravÃs de adsorÃÃo de piridina. O desempenho dos catalisadores foi avaliado na desidrataÃÃo do glicerol, sob fluxo de N2 ou H2, a 1atm e 250ÂC. As mudanÃas na atividade e seletividade devido à troca do gÃs de arraste estÃo associadas a alteraÃÃes nas propriedades Ãcido/redox dos catalisadores, como sugerido pelas medidas de acidez e TPR-H2. AcroleÃna foi o principal produto observado para todos os catalisadores, porÃm a amostra contendo cobre (CuMoAl), mostrou maior atividade catalÃtica e superior seletividade a Ãlcool alÃlico, bem como produÃÃo do 1-propanol; o que està associado a transferÃncia de hidrogÃnio. Essa seletividade concorda com resultados de TPR-H2, que mostram maior influÃncia do cobre sobre a reduÃÃo do Ãxido de molibdÃnio, quando comparado aos promotores (Co ou Ni). Ao final sÃo propostos passos reacionais envolvidos na conversÃo do glicerol a Ãlcool alÃlico.
The economic viability of biodiesel production depends of the use of glycerol, by-product with multifunctional structure, considered a bio-renewable feedstock of great potential to be transformed to fuel or higher value-added chemicals products. In order to contribute to the development of this research area, study was carried out in order to explore the catalytic potential γ-Al2O3 modified with molybdenum oxide and promoter (Cu, Ni or Co) in the glycerol dehydration reaction to chemical intermediates with industrial application was performed. The strategy was to synthesize Al2O3 spheres by hybrid method with interesting structural, textural and chemical properties for then impregnating with precursors of metals via unconventional method (Pechini). The material composition was chosen with the aim of evaluating the bifunctional effect caused by the combination of acid-base and redox properties of molybdenum catalysts supported on alumina. For comparison was evaluated commercial Ni-Mo/Al2O3 catalyst with high acidity and porosidade. The catalysts were characterized for: ICP-OES, XRF, TGA/DTA, XRD, SEM, IR, H2-TPR, TPD-CO2, N2 adsorption/desorption isotherms, and acidity measurements through pyridine adsorption. The catalytic performance was evaluated in the glycerol dehydration under N2 or H2 flow at atmospheric pressure and 250ÂC. The modification in the activity and selectivity due to the change of carrier gas are attributed to the changes of acid/redox properties of the catalyst, as suggested by acidity measurements and TPR-H2. Acrolein was the main product observed for all catalysts, but the cupper containing catalyst (CuMoAl) showed higher catalytic activity and, and superior selectivity to allyl alcohol, as well as the production of 1-propanol, which is due to the hydrogen transfer. This selectivity agrees with H2-TPR results, which show stronger effect of the copper over the molybdenum oxide reduction, if compared to the others promoter (Co or Ni). At the end it is proposed the reaction steps mechanism for the glycerol conversion to allyl alcohol.
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Full textHuang, Chung-wei, and 黃宗煒. "Stereo- and Regioselectivity in Palladium-Catalyzed Allylic Amination by Direct Use of Allyl Alcohols." Thesis, 1999. http://ndltd.ncl.edu.tw/handle/92697331666380599815.
Full text高雄醫學院
藥學研究所
87
Allylic amines are an important class of compounds not only their utility as intermediate in organic synthesis but also because of their physiological properties and their presence in several natural products. Allylation of carbon-, nitrogen-, and oxygen-nucleophiles catalyzed by palladium complexes has been widely applied to organic synthesis. There have been only limited and sporadic reports dealing with the direct cleavage of the C-O bond in allyl alcohols on interaction with a transition metal complex. Precedents of successful applications of a process using allyl alcohols directly to catalytic processes are even more limited. During the course of our studies on the formation of the carbon-nitrogen bond via the O-amination of allyl alcohols in the presence of palladium(0) complexes, we found that the use of anilines as the nucleophiles was a very simple and valuable synthetic route to N-allylanilines. The alkoxides appear to enhance the reactivity of allyl alcohols toward palladium(0) species. We considered that, when anilines are employed as nucleophiles for thereaction, a convenient method to prepare N-allylanilines could be realized; the anilines are useful compounds in organic synthesis. We have examined the reaction of allyl alcohols with anilines in the presence of a palladium catalyst and titanium(IV) isopropoxide. This result prompted us to study in detail the direct use of allyl alcohols with anilines in the presence of a palladium catalyst and titanium(IV) isopropoxide in order to understand the main factors affecting the regio- and stereocontrol of the reaction; this is important for practical synthetic applications and also for gaining more insight into the mechanism.
Jang, Gwo Ming, and 曾國銘. "Microwave Assised Cycloaddition Reaction of Allylic alcohols and Nitrile Oxides." Thesis, 1998. http://ndltd.ncl.edu.tw/handle/74173902127574287473.
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