BENZENE AS a LARVICIDE for SCREW WORMS1 the Larval Stage
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Reactions of Benzene & Its Derivatives
Organic Lecture Series ReactionsReactions ofof BenzeneBenzene && ItsIts DerivativesDerivatives Chapter 22 1 Organic Lecture Series Reactions of Benzene The most characteristic reaction of aromatic compounds is substitution at a ring carbon: Halogenation: FeCl3 H + Cl2 Cl + HCl Chlorobenzene Nitration: H2 SO4 HNO+ HNO3 2 + H2 O Nitrobenzene 2 Organic Lecture Series Reactions of Benzene Sulfonation: H 2 SO4 HSO+ SO3 3 H Benzenesulfonic acid Alkylation: AlX3 H + RX R + HX An alkylbenzene Acylation: O O AlX H + RCX 3 CR + HX An acylbenzene 3 Organic Lecture Series Carbon-Carbon Bond Formations: R RCl AlCl3 Arenes Alkylbenzenes 4 Organic Lecture Series Electrophilic Aromatic Substitution • Electrophilic aromatic substitution: a reaction in which a hydrogen atom of an aromatic ring is replaced by an electrophile H E + + + E + H • In this section: – several common types of electrophiles – how each is generated – the mechanism by which each replaces hydrogen 5 Organic Lecture Series EAS: General Mechanism • A general mechanism slow, rate + determining H Step 1: H + E+ E El e ctro - Resonance-stabilized phile cation intermediate + H fast Step 2: E + H+ E • Key question: What is the electrophile and how is it generated? 6 Organic Lecture Series + + 7 Organic Lecture Series Chlorination Step 1: formation of a chloronium ion Cl Cl + + - - Cl Cl+ Fe Cl Cl Cl Fe Cl Cl Fe Cl4 Cl Cl Chlorine Ferric chloride A molecular complex An ion pair (a Lewis (a Lewis with a positive charge containing a base) acid) on ch lorine ch loronium ion Step 2: attack of -
Summary of Gas Cylinder and Permeation Tube Standard Reference Materials Issued by the National Bureau of Standards
A111D3 TTbS?? o z C/J NBS SPECIAL PUBLICATION 260-108 o ^EAU U.S. DEPARTMENT OF COMMERCE/National Bureau of Standards Standard Reference Materials: Summary of Gas Cylinder and Permeation Tube Standard Reference Materials Issued by the National Bureau of Standards QC 100 U57 R. Mavrodineanu and T. E. Gills 260-108 1987 m he National Bureau of Standards' was established by an act of Congress on March 3, 1901. The Bureau's overall goal i s t0 strengthen and advance the nation's science and technology and facilitate their effective application for public benefit. To this end, the Bureau conducts research to assure international competitiveness and leadership of U.S. industry, science arid technology. NBS work involves development and transfer of measurements, standards and related science and technology, in support of continually improving U.S. productivity, product quality and reliability, innovation and underlying science and engineering. The Bureau's technical work is performed by the National Measurement Laboratory, the National Engineering Laboratory, the Institute for Computer Sciences and Technology, and the Institute for Materials Science and Engineering. The National Measurement Laboratory Provides the national system of physical and chemical measurement; • Basic Standards 2 coordinates the system with measurement systems of other nations and • Radiation Research furnishes essential services leading to accurate and uniform physical and • Chemical Physics chemical measurement throughout the Nation's scientific community, • Analytical Chemistry industry, and commerce; provides advisory and research services to other Government agencies; conducts physical and chemical research; develops, produces, and distributes Standard Reference Materials; provides calibration services; and manages the National Standard Reference Data System. -
Physicochemical Properties of Organic Medicinal Agents
Principles of Drug Action 1, Spring 2005, Esters ESTERS AND RELATED CARBOXYLIC ACID DERIVATIVES Jack DeRuiter I. Structure and Preparation Esters are derivatives of carboxylic acids that arise via replacement of the hydroxyl (OH) portion of the acid COOH function with an "ether" moiety (-OR): O O H C C O C O Acid Ester Note that replacement of the acid OH group with an "ether" moiety removes the acidic function from the parent structure (acid) resulting in the formation of non-acidic (neutral, but somewhat polar) compounds (esters). Esters can be sub-classified based on their general structure as aliphatic, aromatic or cyclic (called "lactones") as illustrated by the examples below: O O CH2CH3 CH2CH3 O CH3 O O O Aliphatic Ester Aromatic Ester Cyclic Ester (Lactone) A variety of methods have been developed for the preparation of esters. Most of these methods involve reaction of an alcohol with an "activated carboxylic acid" compound (i.e. acid chloride): O O H C C X OC C O X- Ester "Activated" acid (X=Cl) Alcohol (Electrophile) (Nucleophile) The ester functionality does not introduce a center of asymmetry and thus optical and geometric isomerism does not result from the presence of this functional group. The ester functionality (the carbonyl and ether oxygen) is composed of an sp2 hybridized carbon so it cannot be chiral, and since there is free rotation about the ether bond geometric isomerism also is not possible at the sp2 center. 1 Principles of Drug Action 1, Spring 2005, Esters II. Solubility of Esters Esters contain carbonyl (C=O) and ether (O-C) dipoles arising from covalent bonding between electronegative oxygen atoms and electronically neutral carbon atoms. -
Halogenated Ether, Alcohol, and Alkane Anesthetics Activate TASK-3 Tandem Pore Potassium Channels Likely Through a Common Mechanism S
Supplemental material to this article can be found at: http://molpharm.aspetjournals.org/content/suppl/2017/03/21/mol.117.108290.DC1 1521-0111/91/6/620–629$25.00 https://doi.org/10.1124/mol.117.108290 MOLECULAR PHARMACOLOGY Mol Pharmacol 91:620–629, June 2017 Copyright ª 2017 by The American Society for Pharmacology and Experimental Therapeutics Halogenated Ether, Alcohol, and Alkane Anesthetics Activate TASK-3 Tandem Pore Potassium Channels Likely through a Common Mechanism s Anita Luethy, James D. Boghosian, Rithu Srikantha, and Joseph F. Cotten Department of Anesthesia, Critical Care, and Pain Medicine, Massachusetts General Hospital, Boston, Massachusetts (A.L., J.D.B., and J.F.C.); Department of Anesthesia, Kantonsspital Aarau, Aarau, Switzerland (A.L.); Carver College of Medicine, University of Iowa, Iowa City, Iowa (R.S.) Received January 7, 2017; accepted March 20, 2017 Downloaded from ABSTRACT The TWIK-related acid-sensitive potassium channel 3 (TASK-3; hydrate (165% [161–176]) . 2,2-dichloro- . 2-chloro 2,2,2- KCNK9) tandem pore potassium channel function is activated by trifluoroethanol . ethanol. Similarly, carbon tetrabromide (296% halogenated anesthetics through binding at a putative anesthetic- [245–346]), carbon tetrachloride (180% [163–196]), and 1,1,1,3,3,3- binding cavity. To understand the pharmacologic requirements for hexafluoropropanol (200% [194–206]) activate TASK-3, whereas molpharm.aspetjournals.org TASK-3 activation, we studied the concentration–response of the larger carbon tetraiodide and a-chloralose inhibit. Clinical TASK-3 to several anesthetics (isoflurane, desflurane, sevoflurane, agents activate TASK-3 with the following rank order efficacy: halothane, a-chloralose, 2,2,2-trichloroethanol [TCE], and chloral halothane (207% [202–212]) . -
Chemistry and Physics of Lipids Effects of Ether Vs. Ester Linkage On
Chemistry and Physics of Lipids 160 (2009) 33–44 Contents lists available at ScienceDirect Chemistry and Physics of Lipids journal homepage: www.elsevier.com/locate/chemphyslip Effects of ether vs. ester linkage on lipid bilayer structure and water permeability S. Deren Guler a, D. Dipon Ghosh b, Jianjun Pan a, John C. Mathai c, Mark L. Zeidel c, John F. Nagle a,b, Stephanie Tristram-Nagle a,∗ a Department of Physics, Carnegie Mellon University, Pittsburgh, PA 15213, USA b Department of Biological Sciences, Carnegie Mellon University, Pittsburgh, PA 15213, USA c Department of Medicine, Beth Israel Deaconess Medical Center and Harvard Medical School, Cambridge, MA 02139, USA article info abstract Article history: The structure and water permeability of bilayers composed of the ether-linked lipid, dihexadecylphos- Received 29 January 2009 phatidylcholine (DHPC), were studied and compared with the ester-linked lipid, dipalmitoylphosphadit- Received in revised form 29 March 2009 dylcholine (DPPC). Wide angle X-ray scattering on oriented bilayers in the fluid phase indicate that the Accepted 26 April 2009 area per lipid A is slightly larger for DHPC than for DPPC. Low angle X-ray scattering yields A = 65.1 Å2 for Available online 3 May 2009 ◦ −13 DHPC at 48 C. LAXS data provide the bending modulus, KC = 4.2 × 10 erg, and the Hamaker parame- ter H =7.2× 10−14 erg for the van der Waals attractive interaction between neighboring bilayers. For the Keywords: low temperature phases with ordered hydrocarbon chains, we confirm the transition from a tilted L Ether lipid ◦ gel phase to an untilted, interdigitated LI phase as the sample hydrates at 20 C. -
Reactions of Aromatic Compounds Just Like an Alkene, Benzene Has Clouds of Electrons Above and Below Its Sigma Bond Framework
Reactions of Aromatic Compounds Just like an alkene, benzene has clouds of electrons above and below its sigma bond framework. Although the electrons are in a stable aromatic system, they are still available for reaction with strong electrophiles. This generates a carbocation which is resonance stabilized (but not aromatic). This cation is called a sigma complex because the electrophile is joined to the benzene ring through a new sigma bond. The sigma complex (also called an arenium ion) is not aromatic since it contains an sp3 carbon (which disrupts the required loop of p orbitals). Ch17 Reactions of Aromatic Compounds (landscape).docx Page1 The loss of aromaticity required to form the sigma complex explains the highly endothermic nature of the first step. (That is why we require strong electrophiles for reaction). The sigma complex wishes to regain its aromaticity, and it may do so by either a reversal of the first step (i.e. regenerate the starting material) or by loss of the proton on the sp3 carbon (leading to a substitution product). When a reaction proceeds this way, it is electrophilic aromatic substitution. There are a wide variety of electrophiles that can be introduced into a benzene ring in this way, and so electrophilic aromatic substitution is a very important method for the synthesis of substituted aromatic compounds. Ch17 Reactions of Aromatic Compounds (landscape).docx Page2 Bromination of Benzene Bromination follows the same general mechanism for the electrophilic aromatic substitution (EAS). Bromine itself is not electrophilic enough to react with benzene. But the addition of a strong Lewis acid (electron pair acceptor), such as FeBr3, catalyses the reaction, and leads to the substitution product. -
Williamson Ether Synthesis the Williamson Ether Synthesis Is an Organic Reaction, Forming an Ether from an Alkyl Halide and an Alcohol
The Williamson ether synthesis The Williamson ether synthesis is an organic reaction, forming an ether from an alkyl halide and an alcohol. This reaction was developed by Alexander Williamson in 1850. It involves the reaction of an alkoxide ion with a primary alkyl halide via an SN2 reaction. The Williamson reaction is widely used in both laboratory and industrial synthesis, and remains the simplest and most popular method of preparing ethers. Both symmetrical and asymmetrical ethers are easily prepared. The reaction for this week: an example of a Williamson ether synthesis acetaminophen ethyl iodide phenacetin starting material reagent product Phenacetin may be synthesized as an example of the Williamson ether synthesis The first synthesis of phenacetin was reported in 1878 by Harmon Morse. Procedure 1. Weigh an Extra-Strength Tylenol tablet. Pulverize the tablet with mortar and pestle. Weigh out 0.22 g and place it in a dry 15-ml round-bottom flask along with 0.28 g of finely pulverized K2CO3 (mortar and pestle) and 3.0 mL of butanone. Carefully add 0.28 mL of ethyl iodide with a syringe. 2. Add a stir bar; attach a microscale water-cooled condenser to the flask. Heat the mixture under reflux directly on a hot plate at medium setting for 1 hour. In the meantime, obtain the IR of acetaminophen. 3. Turn off the heat. Allow the mixture to cool down. Add 4 mL of water to the flask and transfer its contents to a 16 x 125 mm test tube with a screw cap. Rinse round-bottom flask 4 times with 1 mL of tert-butyl methyl ether (BME) and add the rinsings to the test tube. -
Formation of Nitrous Oxide
1461 No. 5069 DECEMBER 24. 1966 NATURE E-+ CCI. --->- ECC1 3 + Cl- Formation of Nitrous Oxide THE mechanism of formation of nitrous oxide from am The tightly bound .CCI3 group will not be removable in monium nitrate is attributable to the recognized thermal the normal biochemical reaction and the enzyme molecule dissociation of ammonium salts followed in this instance will be inactivated. by nitration of ammonia and decomposition of the ensuing This process of enzyme inactivation could, in principle, nitramide. The mechanism of this latter stage has been account for the toxicity of carbon tetrachloride and studied by various workers, notably by Marlies and La similar compounds and also of many insecticides. The Merl. Further, the decomposition of methyl nitramido postulated mechanism would also explain the observation to tho oxide and methyl alcohol is on record 2. by Butlerl3 that carbon tetrachloride is reduced in vivo As the nitration process, for example, of benzene, is to chloroform. Thus a proportion of .CCls radicals may commonly accompanied by some oxidation, the possibility react with sites other than the enzyme and abstract, of its OCClllTcnce in the preparation of nitrous oxide with for example, a hydrogen atom from a hydroxyl group or formation of nitrogen peroxide is not surprising and from a sulphydryl group. The latter exchange does technically well recognized. It has also recently been the appear to be possible from energy considerations. subject of public concern. D(RS-H) = 89 kcalJmole (ref. 14), .J. KENNER D(CI3G-H) = 91·4 kcalJmole (ref. 9) 41 Burlington Road, I have found that the activation energy of the electron Withington, capture reaction in chloroform vapour Manchester 20. -
Reassessment of 3 Tolerance Exemptions for Ethylene Glycol
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY - +,TE* sr4, WASHINGTON, D.C. 20460 Q c, OFFICE OF PREVENTION, PESTICIDES, AND TOXIC SUBSTANCES DATE: June 29,2006 ACTION MEMORANDUM SUBJECT: Reassessment of 3 Tolerance Exemptions for Ethylene Glycol, Diethylene Glycol, and the Combination of Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, and Diethylene Glycol Monobutyl Ether FROM: Pauline Wagner, Chief F b.~!!<Lo 'v \ 3~~10 b Inert Ingredient Assessment Branch Registration Division (7505P) TO: Lois A. Rossi, Director Registration Division (7505P) 1. FQPA REASSESSMENT ACTION Action: Reassessment of three inert exemptions from the requirement of a tolerance. The reassessment decision is to maintain the inert tolerance exemptions "as-is." Table 1. Tolerance Exemptions Being Reassessed in this Document CM~fl,~aa,it Appeara in the CFR CAS iT01muw Registry Number @.I@,- Bxemption $in$@ Uses Name %SOa ,. Exprmsion. Antifreeze, deactivator for all pesticides 107-21-1 920 Ethylene glycol - - - used before crop emerges from soil and in 1,2-Ethanediol herbicides before or after crop emerges Deactivator, adjuvant for formulations used before crop emerges from soil and 11 1-46-6 920 Diethylene glycol --- deactivator for formulations used before Ethanol, 2,2'-oxybis- (9CI) crop emerges from soil, stabilizer Diethylene glycol 1 11-77-3 monomethyl ether Ethanol, 2-(2-methoxyethoxy)- 920 Diethylene glycol monoethyl - - - Deactivator for formulations used before 1 1 1-90-0 ether crop emerges from soil, stabilizer Ethanol, 2-(2-ethoxyethoxy)- Diethylene glycol monobutyl 112-34-5 ether Ethanol, 2-(2-butoxyethoxy)- a. Residues listed in 40 CFR 180.920 are exempted from the requirement of a tolerance when used in accordance with good agricultural practice as inert (or occasionally active) ingredients in pesticide formulations applied to growing crops only. -
Reactions of Alkenes and Alkynes
05 Reactions of Alkenes and Alkynes Polyethylene is the most widely used plastic, making up items such as packing foam, plastic bottles, and plastic utensils (top: © Jon Larson/iStockphoto; middle: GNL Media/Digital Vision/Getty Images, Inc.; bottom: © Lakhesis/iStockphoto). Inset: A model of ethylene. KEY QUESTIONS 5.1 What Are the Characteristic Reactions of Alkenes? 5.8 How Can Alkynes Be Reduced to Alkenes and 5.2 What Is a Reaction Mechanism? Alkanes? 5.3 What Are the Mechanisms of Electrophilic Additions HOW TO to Alkenes? 5.1 How to Draw Mechanisms 5.4 What Are Carbocation Rearrangements? 5.5 What Is Hydroboration–Oxidation of an Alkene? CHEMICAL CONNECTIONS 5.6 How Can an Alkene Be Reduced to an Alkane? 5A Catalytic Cracking and the Importance of Alkenes 5.7 How Can an Acetylide Anion Be Used to Create a New Carbon–Carbon Bond? IN THIS CHAPTER, we begin our systematic study of organic reactions and their mecha- nisms. Reaction mechanisms are step-by-step descriptions of how reactions proceed and are one of the most important unifying concepts in organic chemistry. We use the reactions of alkenes as the vehicle to introduce this concept. 129 130 CHAPTER 5 Reactions of Alkenes and Alkynes 5.1 What Are the Characteristic Reactions of Alkenes? The most characteristic reaction of alkenes is addition to the carbon–carbon double bond in such a way that the pi bond is broken and, in its place, sigma bonds are formed to two new atoms or groups of atoms. Several examples of reactions at the carbon–carbon double bond are shown in Table 5.1, along with the descriptive name(s) associated with each. -
In This Handout, All of Our Functional Groups Are Presented As Condensed Line Formulas, 2D and 3D Formulas and with Nomenclature Prefixes and Suffixes (If Present)
In this handout, all of our functional groups are presented as condensed line formulas, 2D and 3D formulas and with nomenclature prefixes and suffixes (if present). Organic names are built on a foundation of alkanes, alkenes and alkynes. Those examples are presented first and you need to know those rules. The strategies can be found in Chapter 4 of our textbook (alkanes: pages 93-98, cycloalkanes 102-104, alkenes: pages 104-110, alkynes: pages 112-113 and combinations of all of them 113-115). After introducing examples of alkanes, alkenes, alkynes and combinations of them, the functional groups are presented in order of priority. A few nomenclature examples are provided for each of the functional groups. Examples of the various functional groups are presented on pages 115-135 in the textbook. Two overview pages are on pages 136-137. Some functional groups have a suffix name when they are the highest priority functional group and a prefix name when they are not the highest priority group, and these are added to the skeletal names with identifying numbers and stereochemistry terms (E and Z for alkenes, R and S for chiral centers and cis and trans for rings). Several low priority functional groups only have a prefix name. A few additional special patterns are shown on pages 98-102. The only way to learn this topic is practice (over and over). The best practice approach is to actually write out the names (on an extra piece of paper or on a white board, and then do it again). The same functional groups are used throughout the entire course. -
Poly(Arylene Ether)S with Truly Pendant Benzene Sulfonic Acid Groups
Wright State University CORE Scholar Browse all Theses and Dissertations Theses and Dissertations 2008 Poly(arylene ether)s with Truly Pendant Benzene Sulfonic Acid Groups Mohamed Moustafa Abdellatif Wright State University Follow this and additional works at: https://corescholar.libraries.wright.edu/etd_all Part of the Chemistry Commons Repository Citation Abdellatif, Mohamed Moustafa, "Poly(arylene ether)s with Truly Pendant Benzene Sulfonic Acid Groups" (2008). Browse all Theses and Dissertations. 877. https://corescholar.libraries.wright.edu/etd_all/877 This Thesis is brought to you for free and open access by the Theses and Dissertations at CORE Scholar. It has been accepted for inclusion in Browse all Theses and Dissertations by an authorized administrator of CORE Scholar. For more information, please contact [email protected]. POLY(ARYLENE ETHER)S WITH TRULY PENDANT BENZENE SULFONIC ACID GROUPS A thesis submitted in partial fulfillment Of the requirements for the degree of Master of Science By MOHAMED ABDELLATIF B.S. Wright State University, 2006 2008 Wright State University WRIGHT STATE UNIVERSITY SCHOOL OF GRADUATE STUDIES September 4, 2008 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Mohamed Abdellatif ENTITLED Poly(arlyene ether)s with Truly Pendant Benzene Sulfonic Acid Groups BE ACCEPTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science . ______________________________ Eric Fossum, Ph.D. Thesis Director ______________________________ Kenneth Turnbull, Ph.D. Department Chair Committee on Final Examination _________________________________ Eric Fossum, Ph.D. _________________________________ Kenneth Turnbull, Ph.D. _________________________________ Daniel M. Ketcha, Ph.D. _________________________________ Joseph F. Thomas, Jr., Ph.D. Dean, School of Graduate Studies ABSTRACT Abdellatif, M.