Reducing Agents
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Process for Purification of Ethylene Compound Having Fluorine-Containing Organic Group
Office europeen des brevets (fi) Publication number : 0 506 374 A1 @ EUROPEAN PATENT APPLICATION @ Application number: 92302586.0 @ Int. CI.5: C07C 17/38, C07C 21/18 (g) Date of filing : 25.03.92 (30) Priority : 26.03.91 JP 86090/91 (72) Inventor : Kishita, Hirofumi 3-19-1, Isobe, Annaka-shi Gunma-ken (JP) (43) Date of publication of application : Inventor : Sato, Shinichi 30.09.92 Bulletin 92/40 3-5-5, Isobe, Annaka-shi Gunma-ken (JP) Inventor : Fujii, Hideki (84) Designated Contracting States : 3-12-37, Isobe, Annaka-shi DE FR GB Gunma-ken (JP) Inventor : Matsuda, Takashi 791 ~4 YdndSG Anri3k3~shi @ Applicant : SHIN-ETSU CHEMICAL CO., LTD. Gunma-ken (JP) 6-1, Ohtemachi 2-chome Chiyoda-ku Tokyo (JP) @) Representative : Votier, Sidney David et al CARPMAELS & RANSFORD 43, Bloomsbury Square London WC1A 2RA (GB) (54) Process for purification of ethylene compound having fluorine-containing organic group. (57) A process for purifying an ethylene compound having a fluorine-containing organic group (fluorine- containing ethylene compound) by mixing the fluorine-containing ethylene compound with an alkali metal or alkaline earth metal reducing agent, and subjecting the resulting mixture to irradiation with ultraviolet radiation, followed by washing with water. The purification process ensures effective removal of iodides which are sources of molecular iodine, from the fluorine-containing ethylene compound. < h- CO CO o 10 o Q_ LU Jouve, 18, rue Saint-Denis, 75001 PARIS EP 0 506 374 A1 BACKGROUND OF THE INVENTION 1. Field of the Invention 5 The present invention relates to a process for purifying an ethylene compound having a fluorine-containing organic group, and more particularly to a purification process by which iodine contained as impurity in an ethylene compound having a fluorine-containing organic group can be removed effectively. -
Metabolism and Energetics Oxidation of Carbon Atoms of Glucose Is the Major Source of Energy in Aerobic Metabolism
Metabolism and Energetics Oxidation of carbon atoms of glucose is the major source of energy in aerobic metabolism C6H1206 + 6O2 yields 6 CO2 + H20 + energy Energy released ΔG = - 686 kcal/mol Glucose oxidation requires over 25 discrete steps, with production of 36 ATP. Energy Transformations The mitochondrial synthesis of ATP is not stochiometric. Electron–motive force Proton-motive force Phosphoryl-transfer potential in the form of ATP. Substrate level phosphorylation The formation of ATP by substrate-level phosphorylation ADP ATP P CH O P CH2 O P 2 is used to represent HC OH HC OH a phosphate ester: phosphoglycerate CH OH OH CH2 O P kinase 2 P O bisphosphoglycerate 3-phosphoglycerate OH ADP ATP CH2 CH2 CH3 C O P C OH C O pyruvate kinase non-enzymic COOH COOH COOH phosphoenolpyruvate enolpyruvate pyruvate Why ATP? The reaction of ATP hydrolysis is very favorable ΔGo = - 30.5 kJ/mol = - 7.3 kCal/mol 1. Charge separation of closely packed phosphate groups provides electrostatic relief. Mg2+ 2. Inorganic Pi, the product of the reaction, is immediately resonance-stabilized (electron density spreads equally to all oxygens). 3. ADP immediately ionizes giving H+ into a low [H+] environment (pH~7). 4. Both Pi and ADP are more favorably solvated by water than one ATP molecule. 5. ATP is water soluble. The total body content of ATP and ADP is under 350 mmol – about 10 g, BUT … the amount of ATP synthesized and used each day is about 150 mol – about 110 kg. ATP Production - stage 1 - Glycolysis Glycolysis When rapid production of ATP is needed. -
United States Patent 0
1 3,667,923 United States Patent 0 ice Patented June 6, 1972 1 2 ‘I have discovered that anhydrous hydrogen cyanide $667,923 reacts readily with a quaternary ammonium borohydride PREPARATION OF LITHIUM, SODIUM AND and with the borohydrides of lithium and sodium at QUATERNARY AMMONIUM CYANOBORO atmospheric pressure in solvents for the borohydride, such HYDRIDES Robert C. Wade, Ipswich, Mass, assignor to Ventron as glyme, diglyme, triglyme, tetrahydrofuran and dimethyl Corporation, Beverly, Mass. formamide, or mixtures of these at a temperatures be No Drawing. Filed June 16, 1969, Ser. No. 833,722 tween 0° and the boiling point of the solvent to form Int. Cl. C01c 3/08; C01!) 35/00 the corresponding cyanoborohydride. The preferred sol US. Cl. 23-358 4 Claims vents are tetrahydrofuran and glyme because of their 10 convenient boiling points. Potassium borohydride does not react readily with ABSTRACT OF THE DISCLOSURE hydrogen cyanide in tetrahydrofuran or glyme presum The invention relates to the preparation of lithium, ably because of its lack of solubility in these solvents. sodium and quaternary ammonium cyanoborohydrides. However, it reacts with hydrogen cyanide in dimethyl These compounds are prepared by mixing substantially formamide similarly to the other borohydrides mentioned anhydrous hydrogen cyanide with a substantially an above. hydrous lithium or sodium or quaternary ammonium The reaction of the process of the invention appears to borohydride at a temperature between 0° C. and 100° C. take place in two stages. Thus, if the reaction mixture is in a substantially anhydrous solvent, such as tetrahydro initially maintained between about 10° and about 35° C. -
Reductions and Reducing Agents
REDUCTIONS AND REDUCING AGENTS 1 Reductions and Reducing Agents • Basic definition of reduction: Addition of hydrogen or removal of oxygen • Addition of electrons 9:45 AM 2 Reducible Functional Groups 9:45 AM 3 Categories of Common Reducing Agents 9:45 AM 4 Relative Reactivity of Nucleophiles at the Reducible Functional Groups In the absence of any secondary interactions, the carbonyl compounds exhibit the following order of reactivity at the carbonyl This order may however be reversed in the presence of unique secondary interactions inherent in the molecule; interactions that may 9:45 AM be activated by some property of the reacting partner 5 Common Reducing Agents (Borohydrides) Reduction of Amides to Amines 9:45 AM 6 Common Reducing Agents (Borohydrides) Reduction of Carboxylic Acids to Primary Alcohols O 3 R CO2H + BH3 R O B + 3 H 3 2 Acyloxyborane 9:45 AM 7 Common Reducing Agents (Sodium Borohydride) The reductions with NaBH4 are commonly carried out in EtOH (Serving as a protic solvent) Note that nucleophilic attack occurs from the least hindered face of the 8 carbonyl Common Reducing Agents (Lithium Borohydride) The reductions with LiBH4 are commonly carried out in THF or ether Note that nucleophilic attack occurs from the least hindered face of the 9:45 AM 9 carbonyl. Common Reducing Agents (Borohydrides) The Influence of Metal Cations on Reactivity As a result of the differences in reactivity between sodium borohydride and lithium borohydride, chemoselectivity of reduction can be achieved by a judicious choice of reducing agent. 9:45 AM 10 Common Reducing Agents (Sodium Cyanoborohydride) 9:45 AM 11 Common Reducing Agents (Reductive Amination with Sodium Cyanoborohydride) 9:45 AM 12 Lithium Aluminium Hydride Lithium aluminiumhydride reacts the same way as lithium borohydride. -
Part I. the Total Synthesis Of
AN ABSTRACT OF THE THESIS OF Lester Percy Joseph Burton forthe degree of Doctor of Philosophy in Chemistry presentedon March 20, 1981. Title: Part 1 - The Total Synthesis of (±)-Cinnamodialand Related Drimane Sesquiterpenes Part 2 - Photochemical Activation ofthe Carboxyl Group Via NAcy1-2-thionothiazolidines Abstract approved: Redacted for privacy DT. James D. White Part I A total synthesis of the insect antifeedant(±)-cinnamodial ( ) and of the related drimanesesquiterpenes (±)-isodrimenin (67) and (±)-fragrolide (72)are described from the diene diester 49. Hydro- boration of 49 provided the C-6oxygenation and the trans ring junction in the form of alcohol 61. To confirm the stereoselectivity of the hydroboration, 61 was convertedto both (t)-isodrimenin (67) and (±)-fragrolide (72) in 3 steps. A diisobutylaluminum hydride reduction of 61 followed by a pyridiniumchlorochromate oxidation and treatment with lead tetraacetate yielded the dihydrodiacetoxyfuran102. The base induced elimination of acetic acid preceded theepoxidation and provided 106 which contains the desired hydroxy dialdehydefunctionality of cinnamodial in a protected form. The epoxide 106 was opened with methanol to yield the acetal 112. Reduction, hydrolysis and acetylation of 112 yielded (t)- cinnamodial in 19% overall yield. Part II - Various N- acyl- 2- thionothiazolidineswere prepared and photo- lysed in the presence of ethanol to provide the corresponding ethyl esters. The photochemical activation of the carboxyl function via these derivatives appears, for practical purposes, to be restricted tocases where a-keto hydrogen abstraction and subsequent ketene formation is favored by acyl substitution. Part 1 The Total Synthesis of (±)-Cinnamodial and Related Drimane Sesquiterpenes. Part 2 Photochemical Activation of the Carboxyl Group via N-Acy1-2-thionothiazolidines. -
Chapter 20 Electrochemistry
Chapter 20 Electrochemistry Learning goals and key skills: Identify oxidation, reduction, oxidizing agent, and reducing agent in a chemical equation Complete and balance redox equations using the method of half-reactions. Sketch a voltaic cell and identify its cathode, anode, and the directions in which electrons and ions move. o Calculate standard emfs (cell potentials), E cell, from standard reduction potentials. Use reduction potentials to predict whether a redox reaction is spontaneous. o o Relate E cell to DG and equilibrium constants. Calculate emf under nonstandard conditions. Identify the components of common batteries. Describe the construction of a lithium-ion battery and explain how it works. Describe the construction of a fuel cell and explain how it generates electrical energy. Explain how corrosion occurs and how it is prevented by cathodic protection. Describe the reactions in electrolytic cells. Relate the amounts of products and reactants in redox reactions to electrical charge. Electrochemistry Electrochemistry is the study of the relationships between electricity and chemical reactions. • It includes the study of both spontaneous and nonspontaneous processes. 1 Redox reactions: assigning oxidation numbers Oxidation numbers help keep track of what species loses electrons and what species gains them. • An element is oxidized when the oxidation number increases • An element is reduced when the oxidation number decreases • an oxidizing agent causes another element to be oxidized • a reducing agent causes another element to be reduced. Assigning oxidation numbers (sect. 4.4) 1. Elemental form, each atom has ox. # = 0. Zn O2 O3 I2 S8 P4 2. Simple ions, = charge on ion. -1 for Cl-, +2 for Mg2+ 3. -
Journal of Organic Chemistry, 9, 5291 (1944)
[CONTRIBUTIONFROM THE MEDICAL-RESEARCHDIVISION, SHARP AND DOHME,INC. ] STUDIES ON THE LEUCKART REACTION FRANK S. CROSSLEY AND MAURICE L. MOORE Received July 21, 194.4 In 1885, Leuckart (1) first described the conversion of certain aldehydes and ketones to the corresponding amines by heating with excess ammonium formate. Wallach (2) applied the method to a number of alicyclic and terpenoid ketones, as well as certain aldehydes, and showed its general application. Despite the excellent results reported by Wallach, the reaction had found little use by others until Ingersoll (3) and his co-workers published a review of the method and re- ported the synthesis of a series of substituted a-phenethylamines by an improved modification of the procedure. Since the appearance of this publication, other workers have been stimulated to use the reaction in the preparation of a number of amines with varying success. Although the exact mechanism has not been definitely established, the reaction has been studied by Wallach (2) and Ingersoll (4)and explained by the following steps: (a) The ammonium formate dissociates into ammonia and formic acid at the temperature of the reaction; and (b) ammonia adds to the carbonyl group or condenses to form the corresponding imine. (c) The formic acid then acts as a reducing agent to remove the hydroxyl or reduce the imino group; and (d) if in excess, may form the formyl derivative which is subsequently hydrolyzed to the free amine. HCOONH, HCOOH f NHj rR OH 7 R R \ + HCOOH + CHNHz + CO* / R’ H20 R’ R R \ \ CHNHz + HCOOH - CHNHCHO + HzO / / R R Formamide (90-9575) may be substituted for ammonium formate and prob- ably hydrolyzes in the reaction to undergo the same steps as above. -
Ch. 21.1 Redox Reactions and Electrochemical Cells
Pre-Health Post-Baccalaureate Program Study Guide and Practice Problems Course: CHM2046 Textbook Chapter: 21.1 (Silberberg 6e) Topics Covered: Redox Reactions and Electrochemical Cells Created by Isaac Loy 1. Review Understanding this chapter’s material will depend on an in- depth understanding of redox reactions, which were first covered last semester in ch. 4. We will review redox reactions in this study guide, but it would be wise to review ch. 4 if you are having difficulty with this material. Redox reactions will also be incredibly important moving forward into organic chemistry and biochemistry. 2. Oxidation-Reduction Reactions The mnemonic that you will come back to time and time again for this topic is: “LEO the lion says GER” Where “LEO” stands for Loss of Electrons = Oxidation And “GER” stands for Gain of Electrons = Reduction The oxidizing agent (the substance that is being reduced) pulls electrons from the substance that is being oxidized. The reducing agent (the substance that is being oxidized) gives electrons to the substance that is being reduced. Oxidation and reduction are simultaneous processes. In order for a redox reaction to take place, one substance must be oxidized and the other must be reduced. When working with oxidation numbers to solve problems, the substance being oxidized (LEO -> loss of electrons) becomes more positive. Likewise, the substance being reduced (GER -> gaining electrons) becomes more negative. 3. Using Half-Reactions to Solve Redox Problems Follow the steps below to create half-reactions. It is crucial that you follow the steps in order! A. Split up the overall reaction into two half-reactions, where the species of one reaction is being oxidized, and the species of the other reaction is being reduced. -
Aromatic and Aliphatic Amines
Aromatic and Aliphatic Amines 1. Preparation: Amines are prepared by the alkylation of ammonia, Gabriel synthesis, reduction of amides, reduction of nitriles, reduction of nitro-compounds, and reductive amination of aldehydes and ketones. Alkylation of ammonia (Hoffmann,s method): Ethanolic solution of ammonia reacts with an alkyl halide to form primary amine which can further reacts with the alkyl halide to form a secondary amine that can further react to form a tri-substituted amine (i.e., 3o amine). Therefore a mixture of three classes of amines is obtained, alongwith some quaternary ammonium salts. The order of reactivity of halides is RI > RBr > RCl and follow the SN2 pathway. Reduction of alkylazides: A primary amine can be best prepared from alkyl azide by reduction with Na/alcohol or Zn/CH3COOH. Gabriel synthesis: In Gabriel synthesis, phthalimide is converted into its salt potassium phthalimide by the reaction of ethanolic KOH. That salt on heating with an alkyl halide Dr. Debsankar Das, Assistant Prof. P. K. College, Contai Page 1 produces N‐alkyl phthalimide. This can be hydrolyzed by aqueous acids or bases into the primary amine and phthalic acid. Reduction of nitriles: Nitriles can be reduced by lithium aluminum hydride (LiAIH4) or Na/ethanol to primary amines. Reduction of amides: Primary amines can be prepared from amides by reduction with lithium aluminum hydride, while N‐substituted and N, N‐disubstituted amides give secondary and tertiary amines, respectively. Dr. Debsankar Das, Assistant Prof. P. K. College, Contai Page 2 Reduction of nitrocompounds: Aromatic amines are normally prepared by reduction of the corresponding aromatic nitrocompounds with metal/acid or Ni/H2 or LAH. -
Gen Chem II Jasperse Ch. 19 Electrochemistry 1
Gen Chem II Jasperse Ch. 19 Electrochemistry 1 Chapter 19 Electrochemistry Math Summary Relating Standard Cell Potential to Standard Half Cell Potentials Eºcell=Eºoxidation + Eºreduction (standard conditions assume 1.0 M concentrations) Relating Half Cell Potentials when Written in Opposite Directions Eºox = -Eºred for half reactions written in opposite directions Relating Standard Cell Potentials to ∆G ∆Gº = -nFE˚cell (to give answer in kJ, use F = 96.485) F = 96,500 C/mol n=number of electrons transferred Relating Actual Cell Potential to Standard Cell Potential when Concentrations aren't 1.0-M Ecell = Eºcell -[0.0592/n] log Q (Q = ratio of actual concentrations) Relating Standard Cell Potential to Equilibrium Constant log K = nEº/0.0592 Relating Actual Cell Potential to Actual Concentrations in Concentration Cells Ecell = -[0.0592/n] log Q for concentration cells, where anode and cathode differ only in concentration, but otherwise have same ions Relating # of Moles of Electrons Transferred as a Function of Time and Current in Electrolysis 1 mol e- = 96,500 C moles of electrons = [current (A)•time (sec)]/96,500 for electrolysis, moles, current, and time are related. rearranged: time (sec)=(moles of electrons)(96500)/current (in A) Note: 3600 sec/hour so time (hours)=(moles of electrons)(26.8)/current (in A) Electrochemistry-Related Units C = Coulomb = quantity of electrical charge = 6.24 • 1018 electrons • 1 mole of electrons = 96,500 C A = amp = rate of charge flow per time = C/sec V = volt = electrical power/force/strength = J/C 96,500C 96.5 kJ F = Faraday = = mole e− mole e− •V € € Gen Chem II Jasperse Ch. -
Reductive Amination with [11C]Formaldehyde: a Versatile Approach to Radiomethylation of Amines
International Journal of Organic Chemistry, 2012, 2, 202-223 http://dx.doi.org/10.4236/ijoc.2012.23030 Published Online September 2012 (http://www.SciRP.org/journal/ijoc) Reductive Amination with [11C]Formaldehyde: A Versatile Approach to Radiomethylation of Amines Chunying Wu1, Ruoshi Li1, Dorr Dearborn2, Yanming Wang1* 1Division of Radiopharmaceutical Science, Case Center for Imaging Research, Department of Radiology, Cleveland, USA 2Environmental Health, Case Western Reserve University, Cleveland, USA Email: *[email protected] Received February 16, 2012; revised March 24, 2012; accepted April 2, 2012 ABSTRACT Carbon-11 radiolabeled amines constitute a very important class of radioligands that are widely used for positron emis- 11 sion tomography (PET) imaging. Radiolabeling of amines is often achieved through radiomethylation using [ C]CH3I 11 or [ C]CH3OTf under basic conditions in a strictly anhydrous environment. Functional groups such as hydroxyl and carboxyl groups that are often present in the molecules are normally base sensitive and require protection and deprotec- tion, which substantially prolongs and complicates the radiolabeling process. Here we report a versatile approach to a series of C-11 radiolabeled amines prepared through reductive amination using [11C]formaldehyde. Using a variety of substrates bearing different functional groups, we demonstrate the general utility of this method. In contrast to conven- tional radiomethylation methods, the reductive amination using [11C]formaldehyde can be carried out in an aqueous environment relatively quickly without the need of protection of base-sensitive functional groups. Keywords: C-11 Formaldehyde; Radiomethylation; Reductive Amination; Positron Emission Tomography; Radiolabelling 1. Introduction probes must be labeled with positron-emitting radionu- clides such as carbon-11 or fluorine-18. -
Evolution of the First Metabolic Cycles
Proc. Natl. Acad. Sci. USA Vol. 87, pp. 200-204, January 1990 Evolution Evolution of the first metabolic cycles (chemoautotrophy/reductive citric acid cycle/origin of life/pyrite) GUNTER WACHTERSHAUSER 8000 Munich 2, Tal 29, Federal Republic of Germany Communicated by Karl Popper, October 12, 1989 (received for review February 28, 1989) ABSTRACT There are two alternatives concerning the genobacter thermophilus (13), and Desulfobacter hydro- origin of life: the origin may be heterotrophic or autotrophic. genophilus (14) and also in the sulfur-associated archaebac- The central problem within the theory of an autotrophic origin teria Thermoproteus neutrophilus (15) and, partly demon- is the first process of carbon fixation. I here propose the strated, in Sulfolobus brierleyi (16). As suggested by Kandler hypothesis that this process is an autocatalytic cycle that can be and Stetter (16) and previously by Hartmann (17), it may be retrodictively constructed from the extant reductive citric acid considered to be of great antiquity and the evolutionary cycle by replacing thioesters by thioacids and by assuming that precursor ofthe oxidative Krebs cycle. It is here conjectured the required reducing power is obtained from the oxidative to be the extant candidate for the reconstruction of the formation of pyrite (FeS2). This archaic cycle is strictly archaic autocatalytic cycle of carbon fixation. chemoautotrophic: photoautotrophy is not required. The cycle The presently accepted form of the extant reductive citric is catalytic for pyrite formation and autocatalytic for its own acid cycle is shown in Fig. 1 in a somewhat unusual repre- multiplication. It is a consequence of this hypothesis that the sentation, twisted in an 8.