Chapter 12 Problems: 1A,C,E,G,N,O,Q; 2A,B,C,F,G,J,K; 5; 9 A,C,D,E,F,L,M,N; 13 Smith: Chapter 3 March: Chapter 19
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Direct Β‑Functionalization of Cyclic Ketones with Aryl Ketones Via the Merger of Photoredox and Organocatalysis Filip R
Communication pubs.acs.org/JACS Direct β‑Functionalization of Cyclic Ketones with Aryl Ketones via the Merger of Photoredox and Organocatalysis Filip R. Petronijevic,́† Manuel Nappi,† and David W. C. MacMillan* Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States *S Supporting Information ABSTRACT: The direct β-coupling of cyclic ketones with aryl ketones has been achieved via the synergistic combination of photoredox catalysis and organocatalysis. Diaryl oxymethyl or aryl−alkyl oxymethyl radicals, transiently generated via single-electron reduction of ketone precursors, readily merge with β-enaminyl radical species, generated by photon-induced enamine oxidation, to produce γ-hydroxyketone adducts. Experimental evidence indicates that two discrete reaction pathways can be operable in this process depending upon the nature of the ketyl radical precursor and the photocatalyst. he direct β-functionalization of saturated ketones and T aldehydes is an important yet elusive goal in organic chemistry.1 While carbonyl groups are readily amenable to ipso- and α-carbon substitution with a range of nucleophiles and electrophiles respectively,2,3 activation at the β-methylene position poses a significant synthetic challenge. With a few notable exceptions,1,4 carbonyl β-functionalization has tradition- ally been restricted to the conjugate addition of soft nucleophiles are accessed via carbene catalysis,9,10 nucleophilic addition of into α,β-unsaturated carbonyl systems. As such, the development acetal-protected Grignard reagents,11 or stoichiometric metal- 5 − of a general catalytic platform for the direct β-functionalization activated homoenolate equivalents.12 16 of saturated ketones or aldehydes would represent a conceptual Drawing from the mechanistic insights gained in the course of and practical advance for the field. -
Experiment 4
Experiment Limiting Reactant 5 A limiting reactant is the reagent that is completely consumed during a chemical reaction. Once this reagent is consumed the reaction stops. An excess reagent is the reactant that is left over once the limiting reagent is consumed. The maximum theoretical yield of a chemical reaction is dependent upon the limiting reagent thus the one that produces the least amount of product is the limiting reagent. For example, if a 2.00 g sample of ammonia is mixed with 4.00 g of oxygen in the following reaction, use stoichiometry to determine the limiting reagent. 4NH3 + 5O2 4NO + 6H2O Since the 4.00 g of O2 produced the least amount of product, O2 is the limiting reagent. In this experiment you will be given a mixture of two ionic solids, AgNO3 and K2CrO4, that are both soluble in water. When the mixture is dissolved into water they will react to form an insoluble compound, Ag2CrO4, which can be collected and weighed. The reaction is the following: 2 AgNO3(aq) + K2CrO4(aq) Ag2CrO4(s) + 2 KNO3(aq) Colorless Yellow Red colorless Precipitate Precipitate is the term used for an insoluble solid which is produced by mixing two solutions. Often the solid particles are so fine that they will pass right through the pores of a filter. Heating the solution for a while causes the particles to clump together, a process called digesting. The precipitate coagulates upon cooling and eventually settles to the bottom of a solution container. The clear liquid above the precipitate is called the supernatant. -
Study of the Modifications of Manganese Dioxide
U. S. Department of Commerce Research Paper RP1941 National Bureau of Standards Volume 41, December 1948 Part of the Journal of Research of the National Bureau of Standards Study of the Modifications of Mangan,ese Dioxide By Howard F. McMurdie and Esther Golovato P ast work on the modificat ions of manganese dioxide of in terest in dry-cell manufacture is revie wed. New X -ray data, at both room and elevaLcd temperatures, combined 'with differen tial hea ting curves lead to the concl usion that five type of manga nese dioxide exi t : (1) well-crystallized p yrolusite ; (2) gamma m a nganese diox ide, a poorly crystalli zed pyrol u site; (3) ramsdellite ; (4) cryp tomelane, a form co ntaining esse ntial p otassium or sodiulll.; a nd (5) delta m anganese dioxide, belie ved to be a poorly crystallize d cryptomela ne. The high-temperature X-r ay diffraction data indicated the phase cha nges t hat cause the heating curve effects. A new crystal fo rm of manganosic oxide (Mn30 4), stable above 1,1700 C, w ~ s fo und t o be cubic of spinel structure. Fincness dcten n inaLion by both thc nitrogen a dsorp t ion and Lhe X-ray line broadening me thods were made on selected samples. I. Introduction this equipment a fla t specinlen is used, and no During the years 1940- 46 there wa increased special teclmiq Ll es were employed to prcven t pre researeh on dry cells. This was stimulated by fcn 'cd orientation. It is r ealized that in a few increased demand for the cell as well a new u es cascs this may have res ulted in r elative intcnsitics for them , combined with certain hor Lages of raw that differ from those in other r eporLs. -
Review of Calculations for Organic Reactions (Assignment #1B)
Review of Calculations for Organic Reactions (Assignment #1b) In your experiments the quantities of many reactants are given in mass or volume, though chemicals react in mole ratios, because it is not possible to measure a quantity in moles easily. You will have to convert mass or volume (mass = volume x density) to moles before beginning an experiment. You will also have to recognize stoichiometric relationships between reactants and products, which is based on mole ratio, in order to be able to calculate the theoretical yield of product you expect to isolate. You will apply the knowledge from this session to complete the theoretical yield calculation in your prelab reports and postlab reports. In this lab you are expected to be able to differentiate between a limiting reagent and excess reagents, solvents and catalysts which are crucial for the reaction to occur and go to completion. A limiting reagent is a reactant that has the lowest number of moles of all reactants in the chemical reaction and once it is completely consumed the reaction terminates. An excess reagent is a reactant that has a higher number of moles and therefore is not used up when a reaction goes to completion. Solvents and catalysts are not involved in the determination of limiting reagent. An example of calculations that you will be expected to perform is shown using the reaction of phenol with nitric acid. Preparation of picric acid requires the nitration of phenol. Given 5.00 grams of phenol and 15.0 mL concentrated nitric acid (15.9 M), one can determine the MAXIMUM theoretical amount of picric acid formed. -
Aldehydes and Ketones
12 Aldehydes and Ketones Ethanol from alcoholic beverages is first metabolized to acetaldehyde before being broken down further in the body. The reactivity of the carbonyl group of acetaldehyde allows it to bind to proteins in the body, the products of which lead to tissue damage and organ disease. Inset: A model of acetaldehyde. (Novastock/ Stock Connection/Glow Images) KEY QUESTIONS 12.1 What Are Aldehydes and Ketones? 12.8 What Is Keto–Enol Tautomerism? 12.2 How Are Aldehydes and Ketones Named? 12.9 How Are Aldehydes and Ketones Oxidized? 12.3 What Are the Physical Properties of Aldehydes 12.10 How Are Aldehydes and Ketones Reduced? and Ketones? 12.4 What Is the Most Common Reaction Theme of HOW TO Aldehydes and Ketones? 12.1 How to Predict the Product of a Grignard Reaction 12.5 What Are Grignard Reagents, and How Do They 12.2 How to Determine the Reactants Used to React with Aldehydes and Ketones? Synthesize a Hemiacetal or Acetal 12.6 What Are Hemiacetals and Acetals? 12.7 How Do Aldehydes and Ketones React with CHEMICAL CONNECTIONS Ammonia and Amines? 12A A Green Synthesis of Adipic Acid IN THIS AND several of the following chapters, we study the physical and chemical properties of compounds containing the carbonyl group, C O. Because this group is the functional group of aldehydes, ketones, and carboxylic acids and their derivatives, it is one of the most important functional groups in organic chemistry and in the chemistry of biological systems. The chemical properties of the carbonyl group are straightforward, and an understanding of its characteristic reaction themes leads very quickly to an understanding of a wide variety of organic reactions. -
United States Patent (19) (11) 4,055,601 Ehmann 45) Oct
United States Patent (19) (11) 4,055,601 Ehmann 45) Oct. 25, 1977 (54) PROCESS FOR THE OXDATION OF PRIMARY ALLYLCALCOHOLS OTHER PUBLICATIONS Djerassi, "Organic Reactions', vol. VI, chapt. 5, pp. 75 Inventor: William J. Ehmann, Orange Park, 207-234. Fla. Adkins, et al., "J. Amer. Chem. Soc.' vol. 71, pp. (73) Assignee: SCM Corporation, New York, N.Y. 3622-3629. Batty et al., "Chem. Society Journal' (1938), pp. 21 Appl. No.: 582,114 175-179. Filed: May 30, 1975 22 Primary Examiner-Bernard Helfin Related U.S. Application Data Attorney, Agent, or Firm-Richard H. Thomas 63) Continuation-in-part of Ser. No. 437,188, Jan. 28, 1974, 57 ABSTRACT abandoned. Improved conversions of 3-substituted and 3,3-disub (51) Int. Cl’.............................................. CO7C 45/16 stituted allyl alcohols to the corresponding aldehydes (52) U.S. C. ............................ 260/593 R, 260/603 C, are obtained in an Oppenauer oxidation process, under 260/347.8; 260/599; 260/600 R; 260/598 Oppenauer oxidation conditions, by carrying out the (58) Field of Search ............ 260/603 HF, 599, 603 C, oxidation employing furfural as the hydrogen acceptor. 260/593 R, 600 R, 598 The invention is particularly applicable to the oxidation of geraniol and nerol to citral, which can be converted (56) References Cited directly to pseudoionone without purification. U.S. PATENT DOCUMENTS 2,801,266 7/1957 Schinz ........................... 260/603 HF 13 Claims, No Drawings 4,055,601 1. tion produces water as a by-product which hydrolyzes PROCESS FOR THE OXDATION OF PRIMARY and consumes the aluminum catalyst. This requires ALLYLCALCOHOLS nearly stoichiometric quantities (as compared to cata lytic quantities) of the aluminum catalyst (notice page This application is a continuation-in-part of prior 224 of Djerassi, supra). -
Oxidation of Secondary Alcohols to Ketones
Oxidation of secondary alcohols to ketones The oxidation of secondary alcohols to ketones is an important oxidation reaction in organic chemistry. Where a secondary alcohol is oxidised, it is converted to a ketone. The hydrogen from the hydroxyl group is lost along with the hydrogen bonded to the second carbon. The remaining oxygen then forms double bonds with the carbon. This leaves a ketone, as R1–COR2. Ketones cannot normally be oxidised any further because this would involve breaking a C–C bond, which requires too much energy.[1] The reaction can occur using a variety of oxidants. Contents Potassium dichromate PCC (Pyridinium chlorochromate) Dess–Martin oxidation Swern oxidation Oppenauer oxidation Fétizon oxidation See also References Potassium dichromate A secondary alcohol can be oxidised into a ketone using acidified potassium dichromate and heating under 2− 3+ reflux. The orange-red dichromate ion, Cr2O7 , is reduced to the green Cr ion. This reaction was once used in an alcohol breath test. PCC (Pyridinium chlorochromate) PCC, when used in an organic solvent, can be used to oxidise a secondary alcohol into a ketone. It has the advantage of doing so selectively without the tendency to over-oxidise. Dess–Martin oxidation The Dess–Martin periodinane is a mild oxidant for the conversion of alcohols to aldehydes or ketones.[2] The reaction is performed under standard conditions, at room temperature, most often in dichloromethane. The reaction takes between half an hour and two hours to complete. The product is then separated from the spent periodinane.[3] Swern oxidation Swern oxidation oxidises secondary alcohols into ketones using oxalyl chloride and dimethylsulfoxide. -
United States Patent (19) 11, 3,989,755 Mccoy Et Al
United States Patent (19) 11, 3,989,755 McCoy et al. (45) Nov. 2, 1976 54 PRODUCTION OF OXIMES BY THE (56) References Cited REACTION OF CARBON MONOXDE WITH UNITED STATES PATENTS NTROCOMPOUNDS 2,945,065 7/1960 Donaruma...................... 260/566 A 75) Inventors: John J. McCoy, Media; John G. 3,480,672 11/1969 Kober et al..................... 260/566 A Zajacek, Strafford, both of Pa.; Karl 3,734,964 5/1973 Knifton........................... 260/566. A E. Fuger, Therwil, Switzerland (73) Assignee: Atlantic Richfield Company, Los Primary Examiner-Gerald A. Schwartz Angeles, Calif. Attorney, Agent, or Firm-Delbert E. McCaslin 22 Filed: Feb. 20, 1975 (21) Appl. No.: 551,487 57) ABSTRACT Related U.S. Application Data Production of oximes (and ketones) by contacting at 63) Continuation-in-part of Ser. No. 372,457, June 21, elevated temperatures and pressures, a primary or sec 1973, abandoned. ondary saturated aliphatic nitrocompound with carbon monoxide in the presence of a catalyst comprising me 52 U.S. C. ........................ 260/566 A; 260/586 C; tallic selenium or inorganic selenium compounds and 260/586 R; 260/593 R a base. (51 int. Cl”........................................ C07C 131/04 58) Field of Search........ 260/566 A, 586 A, 586 R, 20 Claims, No Drawings 260/593 R 3,989,755 2 cycloaliphatic nitrocompound is contacted with carbon PRODUCTION OF OXIMES BY THE REACTION OF monoxide at temperatures in the range of from 50° to 200 C. under pressures in the range of from 10 atmo CARBON MONOXIDE WITH NITROCOMPOUNDS spheres to 200 atmospheres in the presence of a sele nium catalyst and a base. -
United States Patent Office Patented Nov
3,221,026 United States Patent Office Patented Nov. 30, 1965 2 3,221,026 prepared by reaction of a dicyanoketene acetal of the SALTS OF 1,1-DCYANO-2,2,2-TRIALKOXY formula ETHANES Owen W. Webster, Wilmington, Del, assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Feb. 13, 1962, Ser. No. 172,875 wherein R2 and R3 have the meanings defined above in the 2 Claims. (C. 260-340.9) general formula for the products of this invention, with This invention relates to salts of polycyano compounds, one molar equivalent of an alkali metal alkoxide of an and more particularly, to salts of polycyanopolyalkoxy alcohol having 1-8 carbon atoms at a temperature below ethanes and a process for their preparation. 10° C., and preferably at a temperature between 0 and The salts are derivatives of tetracyanoethylene which -80° C., in the presence of an inert reaction medium, is a very reactive compound that has received considerable e.g., an excess of the alcohol from which the alkoxide is study during the last few years. A large number of new 5 derived, or an ether such as diethyl ether, dioxane, tetra and valuable compounds have been prepared from it, and hydrofuran, ethylene glycol dimethyl ether and the like. now a new class of polycyano compounds is provided by As in the case of the reaction starting with tetracyano the present invention. ethylene, the reaction mixture in this case should also The novel compounds of this invention are salts of the be anhydrous to obtain the best results. -
Synthesis of Novel Single-Source Precursors for CVD of Mixed-Metal Tungsten Oxide
Synthesis of novel single-source precursors for CVD of mixed-metal tungsten oxide Hamid Choujaa A thesis submitted for the degree of Doctor of Philosophy University of Bath Department of Chemistry March 2008 COPYRIGHT Attention is drawn to the fact that copyright of this thesis rests with its author. This copy of the thesis has been supplied on condition that anyone who consults it is understood to recognize that its copyright rests with its author and that no quotation the thesis and no information derived from it may be published without the prior written consent of the author. This thesis may be made available for consultation within the University Library and may be photocopied or lent to other libraries for the purposes of consultation. TABLE OF CONTENTS Abstract ....................................................................................................................................... i Acknowledgements .................................................................................................................... iii Abbreviations and Acronyms .................................................................................................... iv 1. INTRODUCTION .................................................................................................................. 1 1.1 Generality about tungsten(VI) oxide ............................................................................. 1 1.1.1 The different lattice structures of tungsten oxide ........................................... 1 1.1.2 Electronic and -
8.6 Acidity of Alcohols and Thiols 355
08_BRCLoudon_pgs5-1.qxd 12/8/08 11:05 AM Page 355 8.6 ACIDITY OF ALCOHOLS AND THIOLS 355 ural barrier to the passage of ions. However, the hydrocarbon surface of nonactin allows it to enter readily into, and pass through, membranes. Because nonactin binds and thus transports ions, the ion balance crucial to proper cell function is upset, and the cell dies. Ion Channels Ion channels, or “ion gates,” provide passageways for ions into and out of cells. (Recall that ions are not soluble in membrane phospholipids.) The flow of ions is essen- tial for the transmission of nerve impulses and for other biological processes. A typical chan- nel is a large protein molecule imbedded in a cell membrane. Through various mechanisms, ion channels can be opened or closed to regulate the concentration of ions in the interior of the cell. Ions do not diffuse passively through an open channel; rather, an open channel contains regions that bind a specific ion. Such an ion is bound specifically within the channel at one side of the membrane and is somehow expelled from the channel on the other side. Remark- ably, the structures of the ion-binding regions of these channels have much in common with the structures of ionophores such as nonactin. The first X-ray crystal structure of a potassium- ion channel was determined in 1998 by a team of scientists at Rockefeller University led by Prof. Roderick MacKinnon (b. 1956), who shared the 2003 Nobel Prize in Chemistry for this work. The interior of the channel contains binding sites for two potassium ions; these sites are oxygen-rich, much like the interior of nonactin. -
Developing a Method for Determining the Mass Balance of Selenium and Tellurium Bioprocessed by a Selenium-Resistant Bacterium Grown in The
Developing a Method for Determining the Mass Balance of Selenium and Tellurium Bioprocessed by a Selenium-Resistant Bacterium Grown in the Presence of Selenite or Tellurite __________________ A Thesis Presented to The Faculty of the Department of Chemistry Sam Houston State University ____________________ In Partial Fulfillment Of the Requirements for the Degree of Master of Science ____________________ by Janet Horton Bius December, 2001 Developing a Method for Determining the Mass Balance of Selenium and Tellurium Bioprocessed by a Selenium-Resistant Bacterium Grown in the Presence of Selenite or Tellurite by Janet Horton Bius ____________________ Approved: _____________________________ Thomas G. Chasteen ____________________________ Mary F. Plishker ____________________________ Rick C. White Approved: ____________________________ Brian Chapman, Dean College of Arts and Sciences II ABSTRACT Bius, Janet Horton, Developing a Method for Determining the Mass Balance of Selenium and Tellurium Bioprocessed by a Selenium-Resistant Bacterium Grown in the Presence of Selenite or Tellurite, Master of Science (Chemistry), December, 2001. Sam Houston State University, Hunts- ville, Texas, 68 pp. Purpose The purpose of this investigation was to determine: (1) the mass balance of selenium or tellurium that was bioreduced when a selenium-resistant facultative anaerobe was amended with either selenium or tellurium; and (2) methods to analyze for these metalloids in biological samples. Methods Analytical methods were developed for the determination of