SYNTHESIS and PROPERTIES of SOME ARALKYL Hymoperoxides
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Cholesteryl Ester Hydroperoxide Formation in Myoglobin-Catalyzed
Biochemical Pharmacology, Vol. 55, pp. 333–340, 1998. ISSN 0006-2952/98/$19.00 1 0.00 © 1998 Elsevier Science Inc. All rights reserved. PII S0006-2952(97)00470-X Cholesteryl Ester Hydroperoxide Formation in Myoglobin-Catalyzed Low Density Lipoprotein Oxidation CONCERTED ANTIOXIDANT ACTIVITY OF CAFFEIC AND P-COUMARIC ACIDS WITH ASCORBATE Otı´lia Vieira,*† Joa˜o Laranjinha,*† Vı´tor Madeira† and Leonor Almeida*† *LABORATORY OF BIOCHEMISTRY,FACULTY OF PHARMACY; AND †CENTER FOR NEUROSCIENCES, UNIVERSITY OF COIMBRA, 3000 COIMBRA,PORTUGAL ABSTRACT. Two diet-derived phenolic acids, caffeic and p-coumaric acids, interplayed with ascorbate in the protection of low density lipoproteins (LDL) from oxidation promoted by ferrylmyoglobin. Ferrylmyoglobin, a two-electron oxidation product from the reaction of metmyoglobin and H2O2, was able to oxidize LDL, degrading free cholesterol and cholesteryl esters. Upon exposure to ferrylmyoglobin, LDL became rapidly depleted of cholesteryl arachidonate and linoleate, which turn into the corresponding hydroperoxides. Cholesteryl oleate and cholesterol were, comparatively, more resistant to oxidation. Caffeic (2 mM) and p-coumaric (12 mM) acids efficiently delayed oxidations, as reflected by an increase in the lag times required for linoleate hydroperoxide and 7-ketocholesterol formation as well as for cholesteryl linoleate consumption. At the same concentration, ascorbate, a standard water-soluble antioxidant, was less efficient than the phenolic acids. Additionally, phenolic acids afforded a protection to LDL that, conversely to ascorbate, extends along the time, as inferred from the high levels of cholesteryl linoleate and cholesteryl arachidonate left after 22 hr of oxidation challenging. Significantly, the coincubation of LDL with ascorbate and each of the phenolic acids resulted in a synergistic protection from oxidation. -
One-Pot Syntheses of Irida-Polycyclic Aromatic Hydrocarbons† Cite This: Chem
Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue One-pot syntheses of irida-polycyclic aromatic hydrocarbons† Cite this: Chem. Sci.,2019,10, 10894 a a a b a All publication charges for this article Yu Xuan Hu,‡ Jing Zhang,‡ Xiaoyan Wang, Zhengyu Lu, Fangfang Zhang, have been paid for by the Royal Society Xiaofei Yang,a Zhihua Ma,a Jun Yin, *a Haiping Xia b and Sheng Hua Liu *a of Chemistry Metalla-analogues of polycyclic aromatic hydrocarbons (PAHs) have captivated chemists with their fascinating structures and unique electronic properties. To date, metallabenzene, metallanaphthalene and metallaanthracene have been reported. Metalla-analogues with more complicated fused rings have rarely been reported. Herein, we have successfully synthesized a series of new iridafluoranthenes and fused-ring iridafluoranthenes ranging from pentacyclic to heptacyclic metallaaromatic hydrocarbons in Received 6th August 2019 high yields under mild reaction conditions for the first time. Their photophysical and redox properties Accepted 12th October 2019 were also explored using UV-vis spectroscopy and electrochemistry combined with TD-DFT DOI: 10.1039/c9sc03914g calculations. The present work may offer an important guideline for the design and construction of new rsc.li/chemical-science polycyclic metallaaromatic hydrocarbons and metalla-nanographenes. Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Introduction carbeneiridium compound by using an intramolecular C–H activation reaction.6b In 2018, they further developed irida- Polycyclic aromatic hydrocarbons (PAHs), as important compo- phenanthrene, iridanaphthalene and iridaanthracene from nents in the eld of organic chemistry, have attracted a signi- their corresponding methoxy(alkenyl)carbeneiridium inter- * cant amount of attention due to their wide range of applications mediates via reactions of [IrCp Cl(NCMe) (PMe3)]PF6 with 8 in organic light-emitting diodes,1 eld-effect transistors2 and diarylpropargyl alcohols. -
Epoxidations and Hydroperoxidations of A,ß-Unsaturated Ketones
Springer Theses Epoxidations and Hydroperoxidations of a,ß-Unsaturated Ketones An Approach through Asymmetric Organocatalysis Bearbeitet von Corinna Reisinger 1. Auflage 2012. Buch. xvi, 260 S. Hardcover ISBN 978 3 642 28117 4 Format (B x L): 15,5 x 23,5 cm Gewicht: 578 g Weitere Fachgebiete > Chemie, Biowissenschaften, Agrarwissenschaften > Analytische Chemie > Organische Chemie Zu Inhaltsverzeichnis schnell und portofrei erhältlich bei Die Online-Fachbuchhandlung beck-shop.de ist spezialisiert auf Fachbücher, insbesondere Recht, Steuern und Wirtschaft. Im Sortiment finden Sie alle Medien (Bücher, Zeitschriften, CDs, eBooks, etc.) aller Verlage. Ergänzt wird das Programm durch Services wie Neuerscheinungsdienst oder Zusammenstellungen von Büchern zu Sonderpreisen. Der Shop führt mehr als 8 Millionen Produkte. Chapter 2 Background 2.1 Asymmetric Organocatalysis For a long time, the realm of asymmetric catalysis was dominated by metal and biocatalysis. Yet, at the beginning of this century, List’s discovery of the (S)-proline- catalyzed direct asymmetric intermolecular aldol reaction [1] together with the development of an asymmetric Diels–Alder reaction catalyzed by a chiral imidazo- lidinone salt by MacMillan et al. [2] have raised awareness of the potential of purely organic molecules as efficient catalysts for a variety of asymmetric transformations and brought to life the term ‘‘organocatalysis’’ to address this research field (Scheme 2.1). 2.1.1 Historical Development Organocatalysis has a rich background as it is suggested that extraterrestrial, enantiomerically enriched amino acids such as (S)-alanine and (S)-isovaline played a decisive role in the prebiotic formation of key building blocks such as sugars by promoting the self-aldol reaction of glycolaldehydes in water [3]. -
Newly Observed Peroxides and the Water Effect on the Formation And
EGU Journal Logos (RGB) Open Access Open Access Open Access Advances in Annales Nonlinear Processes Geosciences Geophysicae in Geophysics Open Access Open Access Natural Hazards Natural Hazards and Earth System and Earth System Sciences Sciences Discussions Open Access Open Access Atmos. Chem. Phys., 13, 5671–5683, 2013 Atmospheric Atmospheric www.atmos-chem-phys.net/13/5671/2013/ doi:10.5194/acp-13-5671-2013 Chemistry Chemistry © Author(s) 2013. CC Attribution 3.0 License. and Physics and Physics Discussions Open Access Open Access Atmospheric Atmospheric Measurement Measurement Techniques Techniques Discussions Open Access Newly observed peroxides and the water effect on the formation and Open Access removal of hydroxyalkyl hydroperoxides in the ozonolysis of Biogeosciences Biogeosciences isoprene Discussions D. Huang, Z. M. Chen, Y. Zhao, and H. Liang Open Access Open Access State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Climate Engineering, Peking University, Beijing 100871, China Climate of the Past of the Past Correspondence to: Z. M. Chen ([email protected]) Discussions Received: 5 January 2013 – Published in Atmos. Chem. Phys. Discuss.: 25 February 2013 Open Access Open Access Revised: 4 May 2013 – Accepted: 15 May 2013 – Published: 12 June 2013 Earth System Earth System Dynamics Dynamics Abstract. The ozonolysis of alkenes is considered to be an lows them to become involved in atmospheric chemical pro- Discussions important source of atmospheric peroxides, which serve as cesses, e.g., SOA formation and radical recycling. oxidants, reservoirs of HOx radicals, and components of sec- Open Access ondary organic aerosols (SOAs). Recent laboratory investi- Geoscientific Geoscientific Open Access gations of this reaction identified hydrogen peroxide (H2O2) Instrumentation Instrumentation and hydroxymethyl hydroperoxide (HMHP) in ozonolysis 1 Introduction Methods and Methods and of isoprene. -
T-Hydro Tert-Butyl Hydroperoxide (TBHP) Product Safety Bulletin
T-Hydro Tert-Butyl Hydroperoxide (TBHP) Product Safety Bulletin lyondellbasell.com Foreword Lyondell Chemical Company (“Lyondell”), a LyondellBasell company, This Product Safety Bulletin should be evaluated to determine applicability is dedicated to continuous improvement in product health, safety and to your specific requirements. Please make sure you review the environmental performance. Included in this effort is a commitment to government regulations, industry standards and guidelines cited in this support our customers by providing guidance and information on the safe bulletin that might have an impact on your operations. use of our products. For Lyondell, environmentally sound operations, like Lyondell is ready to support our customers’ safe use of our products. For environmentally sound products, make good business sense. additional information and assistance, please contact your LyondellBasell Lyondell Product Safety Bulletins are prepared by our Environmental, customer representative. Health and Safety Department with the help of experts from our LyondellBasell is a member of SPI’s Organic Peroxide Producers Safety manufacturing and research facilities. The data reflect the best Division (OPPSD). information available from public and industry sources. This document is provided to support the safe handling, use, storage, transportation and March 2016 ultimate disposal of our chemical products. Telephone numbers for transportation emergencies: CHEMTREC +1-800-424-9300 International (call collect) +1-703-527-3887 or CANUTEC (in Canada) -
Organic & Biomolecular Chemistry
Organic & Biomolecular Chemistry Accepted Manuscript This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. www.rsc.org/obc Page 1 of 12 Organic & Biomolecular Chemistry Journal Name RSCPublishing ARTICLE A Powerful Combination: Recent Achievements on Using TBAI and TBHP as Oxidation System Cite this: DOI: 10.1039/x0xx00000x Xiao-Feng Wu,a,b* Jin-Long Gong,a and Xinxin Qia Manuscript Received 00th January 2012, The recent achievements on using TBAI (tetrabutylammonium iodide) and TBHP (tert-butyl Accepted 00th January 2012 hydroperoxide) as oxidation system have been summarized and discussed. DOI: 10.1039/x0xx00000x www.rsc.org/ Introduction Accepted Oxidative transformation is one of the fundamental reactions in TBAI-catalyzed C-C bonds formation modern organic synthesis, which have experienced impressive [1] progress during the last decades. -
Detection of Phenethylamine, Amphetamine, and Tryptamine Imine By-Products from an Acetone Extraction
Detection of Phenethylamine, Amphetamine, and Tryptamine Imine By-Products from an Acetone Extraction Mary A. Yohannan* and Arthur Berrier U.S. Department of Justice Drug Enforcement Administration Special Testing and Research Laboratory 22624 Dulles Summit Court Dulles, VA 20166 [email: mary.a.yohannan -at- usdoj.gov] ABSTRACT: The formation of imine by-products from phenethylamines, amphetamines, and tryptamines upon an acetone extraction is presented. These imine by-products were characterized using GC/MSD and exhibited preferential cleavage at the α-carbon of the alkyl chain. Further characterization of the imine by-products of phenethylamine and tryptamine was done using IR and NMR. KEYWORDS: phenethylamine, tryptamine, imine, acetone, schiff base, drug chemistry, forensic chemistry In most forensic laboratories, the solvents used to extract at the α-carbon on the alkyl chain. In addition to GC/MS, the drugs are chosen based upon their solubility properties and their imines formed from phenethylamine base and tryptamine base ability to not interact with the drug. In fact, there are very few were characterized by Fourier transform-infrared spectroscopy publications where a solvent used to extract a drug reacts with (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. the drug and forms by-products [1-3]. This laboratory recently discovered that an additional Experimental component was formed when acetone was used to extract a Solvents, Chemicals, and Materials sample containing a known tryptamine. Analysis by gas Acetone was ACS/HPLC grade from Burdick and Jackson chromatography/mass spectroscopy (GC/MS) of the acetone Laboratories (Muskegon, MI). Phenethylamine base and extract yielded an extra peak in the total ion chromatogram that tryptamine base were obtained from Sigma-Aldrich Chemicals was approximately half the abundance of the known tryptamine (Milwaukee, WI). -
Asymmetric Epoxidation of Electron-Deficient Olefins
186 Current Organic Synthesis, 2008, 5, 186-216 Asymmetric Epoxidation of Electron-Deficient Olefins David Díez*, Marta G. Núñez, Ana B. Antón, P. García, R.F. Moro, N.M. Garrido, Isidro S. Marcos, P. Basabe and Julio G. Urones Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad de Salamanca, 37006 Salamanca, Spain Abstract: This paper focuses on the latest developments in asymmetric epoxidation of electron-deficient olefins since the review by Por- ter and Skidmore on chiral ligand-metal peroxide systems, polyamino acid catalysed and organocatalysed epoxidations. Particular atten- tion has been paid to the most recent advances using chiral pyrrolidines as organocatalysts. Key Words: Asymmetric epoxidation, electron deficient olefins, organocatalysis, dioxiranes, chiral ligand–metal peroxide systems, Juliá- Colonna epoxidation. Dedicated to Prof. M. Yus on the occasion of his 60th birthday. 1. INTRODUCTION years only two of them appear to have remained interesting among An excellent review on the asymmetric epoxidation of electron- synthetic organic chemists: the use of tartrates and BINOL 1 as deficient olefins was published in 2000 by Porter and Skidmore [1]. ligands (Fig. 1). Since then, there have been several important developments in this area, especially the use of chiral pyrrolidines as organocatalysts. This review is an update of the one by Porter and Skidmore. ROOC OH From the work of Weitz-Scheffer on epoxidation of electron- OH OH deficient carbonyl compounds [2] using alkaline H2O2, much pro- gress has been made towards the development of an asymmetric OH OH OH variant. The resulting enantiomerically enriched epoxy compounds ROOC can be easily transformed into many types of useful chiral com- pounds [3]. -
Toxic Aldehyde Generation in and Food Uptake from Culinary Oils
www.nature.com/scientificreports OPEN Toxic aldehyde generation in and food uptake from culinary oils during frying practices: Received: 30 May 2017 Accepted: 14 December 2018 peroxidative resistance of a Published: xx xx xxxx monounsaturate-rich algae oil Sarah Moumtaz, Benita C. Percival, Devki Parmar, Kerry L. Grootveld, Pim Jansson & Martin Grootveld Human ingestion of cytotoxic and genotoxic aldehydes potentially induces deleterious health efects, and high concentrations of these secondary lipid oxidation products (LOPs) are generated in polyunsaturated fatty acid (PUFA)-rich culinary oils during high temperature frying practices. Here, we explored the peroxidative resistance of a novel monounsaturate-rich algae frying oil (MRAFO) during laboratory-simulated shallow- and domestically-based repetitive deep-frying episodes (LSSFEs and DBRDFEs respectively), the latter featuring potato chip fryings. Culinary frying oils underwent LSSFEs at 180 °C, and DBRDFEs at 170 °C: aldehydes were determined by 1H NMR analysis in samples collected at increasing heating/frying time-points. Fast food restaurant-fried potato chip serving (FFRPCS) aldehyde contents were also monitored. Substantially lower levels of aldehydes were generated in the MRAFO product than those observed in PUFA-richer oils during LSSFEs. Toxicologically-signifcant concentrations of aldehydes were detected in FFRPCSs, and potato chips exposed to DBRDFEs when using a PUFA-laden sunfower oil frying medium: these contents increased with augmented deep-frying episode repetition. FFRPCS aldehyde contents were 10–25 ppm for each class monitored. In conclusion, the MRAFO product generated markedly lower levels of food-penetrative, toxic aldehydes than PUFA- rich ones during LSSFEs. Since FFRPCS and DBRDFE potato chip aldehydes are predominantly frying oil-derived, PUFA-deplete MRAFOs potentially ofer health-friendly advantages. -
Gas Phase Ion/Molecule Reactions As Studied by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry
INIS-mf—10165 GAS PHASE ION/MOLECULE REACTIONS AS STUDIED BY FOURIER TRANSFORM ION CYCLOTRON RESONANCE MASS SPECTROMETRY STEEN INGEMANN J0RGENSEN GAS PHASE ION/MOLECULE REACTIONS AS STUDIED BY FOURIER TRANSFORM ION CYCLOTRON RESONANCE MASS SPECTROMETRY ACADEMISCH PROEFSCHRIFT ter verkrijging van de graad van doctor in de Wiskunde en Natuurwetenschappen aan de Universiteit van Amsterdam, op gezag van de Rector Magnificus dr. D.W. Bresters, hoogleraar in de Faculteit der Wiskunde en Natuurwetenschappen, in het openbaar te verdedigen in de Aula der Universiteit (tijdelijk in het Wiskundegebouw, Roetersstraat 15) op woensdag 12 juni 1985 te 16.00 uur. door STEEN INGEMANN J0RGENSEN geboren te Kopenhagen 1985 Offsetdrukkerij Kanters B.V., Alblasserdam PROMOTOR: Prof. Dr. N.M.M. Nibbering Part of the work described in this thesis has been accomplished under the auspices of the Netherlands Foundation for Chemical Research (SON) with the financial support from the Netherlands Organization for the Advancement of Pure Research (ZWO). STELLINGEN 1. De door White e.a. getrokken conclusie, dat het cycloheptatrieen anion omlegt tot het benzyl anion in de gasfase, is onvoldoende ondersteund door de experimentele gegevens. R.L. White, CL. Wilkins, J.J. Heitkamp, S.W. Staley, J. Am. Chem. Soc, _105, 4868 (1983). 2. De gegeven experimentele methode voor de lithiëring van endo- en exo- -5-norborneen-2,3-dicarboximide is niet in overeenstemming met de ge- postuleerde vorming van een algemeen dianion van deze verbindingen. P.J. Garratt, F. Hollowood, J. Org. Chem., 47, 68 (1982). 3. De door Barton e.a. gegeven verklaring voor de observaties, dat O-alkyl- -S-alkyl-dithiocarbonaten reageren met N^-dimethylhydrazine onder vor- ming van ^-alkyl-thiocarbamaten en ^-alkyl-thiocarbazaten, terwijl al- koxythiocarbonylimidazolen uitsluitend £-alkyl-thiocarbazaten geven, is hoogst twijfelachtig. -
Peroxides and Peroxide- Forming Compounds
FEATURE Peroxides and peroxide- forming compounds By Donald E. Clark Bretherick5 included a discussion of nated. However, concentrated hydro- organic peroxide5 in a chapter on gen peroxide (Ͼ30%), in contact with norganic and organic peroxides, highly reactive and unstable com- ordinary combustible materials (e.g., because of their exceptional reac- pounds and used “oxygen balance” to fabric, oil, wood, or some resins) Itivity and oxidative potential are predict the stability of individual com- poses significant fire or explosion haz- widely used in research laboratories. pounds and to assess the hazard po- ards. Peroxides of alkali metals are not This review is intended to serve as a tential of an oxidative reaction. Jack- particularly shock sensitive, but can 6 guide to the hazards and safety issues son et al. addressed the use of decompose slowly in the presence of associated with the laboratory use, peroxidizable chemicals in the re- moisture and may react violently with handling, and storage of inorganic and search laboratory and published rec- a variety of substances, including wa- organic peroxy-compounds and per- ommendations for maximum storage ter. Thus, the standard iodide test for oxide-forming compounds. time for common peroxide-forming peroxides must not be used with these The relatively weak oxygen-oxygen laboratory solvents. Several solvents, water-reactive compounds.1 linkage (bond-dissociation energy of (e.g., diethyl ether) commonly used in Inorganic peroxides are used as ox- 20 to 50 kcal moleϪ1) is the character- the laboratory can form explosive re- idizing agents for digestion of organic istic structure of organic and inor- action products through a relatively samples and in the synthesis of or- ganic peroxide molecules, and is the slow oxidation process in the pres- ganic peroxides. -
The Synthesis and Characterisation of a New Tröger's Base Content
Sys Rev Pharm 2020;11(7):319-323 A multifaceted review journal in the field of pharmacy The Synthesis and Characterisation of a New Tröger’s Base Content Methoxy Group Sadiq A. Karim1, Mohammed H. Said2, Jinan A. Abd3, Asim A. Balakit4, Ayad F. Alkaim5 1,2,5Chemistry department, College of Science for women, University of Babylon, Iraq. 3Department of Laser physics, College of Science for women, University of Babylon, Iraq. 4Pharmaceutical Chemistry department, College of Pharmacy, University of Babylon, Iraq. Corresponding author: [email protected] ABSTRACT Five Tröger’s base (TB) molecules were synthesized by reaction aniline’s Keywords: Tröger base, heterocyclic compounds, chirality derivatives which content a methoxy group with a supplement of methylene (dimethoxymethane (DMM)) in present trifluoroacetic acid (TFA) as a solvent Correspondence: and catalyst. This method afforded a good ratio product between 62% to 99%, Sadiq A. Karim1 all products were conforming by FTIR, HRMs, 1HNMR, 13CNMR, and XRD. 1,2,5Chemistry department, College of Science for women, University of Babylon, Iraq. Corresponding author: [email protected] INTRODUCTION collected by filtration and was dried in a vacuum oven at The first Tröger’s base was create in 1887 by Julius Tröger 50 °C for 2 h. during his Ph.D. studied, this compound was called Tröger base 1 (TB1) which from the condensation of methanal 1- Synthesis of 2,9-Dimethoxy-6H,12H-5,11- with 4-aminotoluene in HCl-catalysed media.1 The TB1 methanodibenzo[b,f](1,5)diazocine (TB-OCH3-1) (2,8-dimethyl-6H,12H-5,11- General procedure was followed using m-anisidine (9.1 methanodibenzo[b,f][1,5]diazocine) was conformed ml, 10.00 g, 81.20 mmol), DMM (10.8 ml, 9.269 g, 121.80 structure through chemical reaction by M.