DOCSLIB.ORG

Lab9 Methyl Benzoate Handout1

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Lab9 Methyl Benzoate Handout1 Handout Esterification and Acetalization 1) Fischer Esterification: O O OH conc. H2SO4 OMe + xs MeOH + H2O benzoic acid methyl benzoate Example: esterification of benzoic acid to methyl benzoate. MECHANISM (Fischer esterification) H O O H H H O O R OH R OH H H R O R O Carboxylic Acid R'OH H H O O H OH R R OH R OH OR' O O R' R' H O Equilibrium displaced by either 1) water removal + H 2) ester distillation R OR' 3) excess alcohol Ester The overall process of esterification is one involving an equilibrium among a variety of compounds, and for the reaction to give a high yield; the equilibrium must be shifted toward the products: the desired ester, and water. This can be accomplished either by removing one or more of the products from the reaction mixture as they are formed or by using a large excess of one of the starting reagents. The effect of the latter approach is obvious from consideration of the mass law relating starting materials and products (equation). Increasing the amount of either the alcohol or the carboxylic acid will result in an increase in the amount of products formed since the equilibrium constant. K, for the reaction-must remain constant at a given temperature, no matter what quantity of either reagent is used. Removing water is also a strategy and drying agents can be used, or azeotropic distillation. However, azeotropic distillation is not possible for all alcohols. O K O + R'OH + H2O R OH R OR' [RCOOR'] [H2O] K = [RCOOH] [R'OH] Problem Assignment THIS PROBLEM MUST BE ANSWERED IN YOUR NOTEBOOK AND WILL BE PART OF YOUR GRADE Assuming the equilibrium constant for the esterification of benzoic with methanol is K = 3, calculate the theoretical yield of methyl benzoate expected using the following conditions: 6.1 g of benzoic acid and 20 mL of methanol, and 2 mL of concentrated sulfuric acid. Concentrated sulfuric acid is added as a catalyst in the esterification procedure, even though another acid (benzoic acid) is one of the organic reagents used. Why is the sulfuric acid necessary? Azeotropes can be distilled using a Dean-Stark trap. If the azeotrope separates into two phases upon cooling, then water can be removed. This is the case with water/toluene and water/benzene (among other). For example benzoic acid + n-BuOH can be esterified (with H2SO4) as a catalyst, without using a large excess of alcohol. Think about how the Dean-Stark trap (glassware below) might work. Distillation of azeotropes To remove water as it is forming, a drying agent can be used, or a Dean-Stark apparatus if the solvent forms an azeotrope Distilling receiver - Dean-Stark apparatus EQUILIBRIA, RATES, ENERGY DIAGRAMS, MECHANISMS JLM/05 EQUILIBRIA, RATES, ENERGY DIAGRAMS, MECHANISMS o TABLE: Relationship between Keq and !G Note: at 25oC, the value of 2.3RT is about o More stable 1.4 kcal/mol !G K (kcal/mol) eq state (%) 0 1 50 0.1 1.2 54.5 Relationship Between Energy Difference and Distribution 0.24 1.5 60 100 0.5 2.4 69.7 0.82 4.0 80 90 1 5.4 84.4 1.30 9 90 2 29.3 96.7 state 80 2.72 99 99 stable 70 5 4631 99.98 more 7 10 2.1 x 10 99.999996 of % o o !G = -RT lnK !G = -2.3RT logK 60 -!Go/RT -!Go/2.3RT 50 K = e K = 10 0 1 2 3 4 5 6 Free energy difference (kcal/mol) Le Chatelier’s Principle: a system at equilibrium responds to a disturbance/stress so as to mi nimize the disturbance/stress.Le Chatelier’s Principle: a system at equilibrium responds to a disturbance/stress so as to minimize the disturbance/stress. 2) Acetalization (acetal formation) TABLE: Approximate A Values (Free Energy Difference between Equatorial & Axial Substituents on a Cyclohexane Ring O 2 ROH RO OR ACETAL FORMATION + R1 R2 cat. H R1 R2 H H H H O R O Approx.O O Approx. HO O R HApprox.O Functional o Functional o Functional o + H !G !G R !GR GroupR R R R Group R1 RGroup2 1 2 1 2 kcal/mol1 2 R1 R2 kcal/mol kcal/mol hemiacetal HgClpKa - 5 to -10 - 0.25 OMe 0.6 CH=CH2 1.7 HgBr 0.0 R OHOH (protic sol) 0.9-1.0 CH3 1.8H CN 0.15-0.25 OH (aprotic sol) 0.5-0.6 C2H5 1.8 R R H H F H 0.25 NOO2 1.1 i-Pr 2.1O R R O O R O + O I 0.46 SPh 1.1-1.2 C6HO 11 H 2.2 R R R R H R R Br 1 0.52 -0.6 COOEt1 2 1.1R-1.21 R2 Me3Si 12.5 2 OTs 0.51 COOMe 1.3 Ph 2.8 Cl - H0.52 COOH R OH1.4 t-Bu 4.9 OAc 0.71 NH2 1.4 RO OR This reaction is reversible, so acetal hydrolysis has the same mechanism R1 R2 going in the backward direction. acetal The equilibria are controlled by either removal of water or by using an excess of reagents (water or alcohol) RO OR H2O O ACETAL HYDROLYSIS R R + 1 2 cat. H R1 R2 Related reaction: alcohol protection to ROTHP (THP = tetrahydropyranyl) H H H because of this resonance O O O stabilization the isomer does not form O H DHP less stable (dihydropyran) R OH + H H O O O O R R ROTHP Related reaction: enol ether hydrolysis R H RO H RO O H2O O R O H O H H H H same intermediates as above Hemiacetal: HEMIACETALS ACETALS OH OH H H H OH H H O O H O HO HO HO H H H OH H H H OR OH OH H OH OH OH OH H OH (disaccharide, polysaccharide) !-pyranose -pyranose " R = sugar carbohydrates: [C(H2O)]n JLM/05 EQUILIBRIA, RATES, ENERGY DIAGRAMS, MECHANISMS o TABLE: Relationship between Keq and !G Note: at 25oC, the value of 2.3RT is about !Go More stable 1.4 kcal/mol K (kcal/mol) eq state (%) 0 1 50 0.1 1.2 54.5 Relationship Between Energy Difference and Distribution 0.24 1.5 60 100 0.5 2.4 69.7 0.82 4.0 80 90 1 5.4 84.4 1.30 9 90 state 80 2 29.3 96.7 stable 70 2.72 99 99 more of 5 4631 99.98 % 7 10 2.1 x 10 99.999996 60 !Go = -RT lnK !Go = -2.3RT logK 50 o o 0 1 2 3 4 5 6 -!G /RT -!G /2.3RT Free energy difference (kcal/mol) K = e K = 10 The Anomeric Effect Le Chatelier’s Principle: a system at equilibrium responds to a disturbance/stress so as to Conformational analysis of cyclohexanesminimize the disturbance/stress. TABLE: Approximate A Values (Free Energy Difference between Equatorial & Axial Substituents on a Cyclohexane Ring FG equatorial axial FG FG = functional group Approx. Approx. Approx. Functional Functional Functional !Go !Go !Go Group Group Group kcal/mol kcal/mol kcal/mol HgCl - 0.25 OMe 0.6 CH=CH2 1.7 HgBr 0.0 OH (protic sol) 0.9-1.0 CH3 1.8 CN 0.15-0.25 OH (aprotic sol) 0.5-0.6 C2H5 1.8 F 0.25 NO2 1.1 i-Pr 2.1 I 0.46 SPh 1.1-1.2 C6H11 2.2 Br 0.5-0.6 COOEt 1.1-1.2 Me3Si 2.5 OTs 0.51 COOMe 1.3 Ph 2.8 Cl 0.52 COOH 1.4 t-Bu 4.9 OAc 0.71 NH2 1.4 ANOMERIC EFFECT O O when X is electronegative X (OH, OR, Cl, etc.) then the axial conformation is more stable X equatorial axial Origin of the anomeric effect: the lone pair on the ring oxygen (HOMO) interacts with the C-X antibonding orbital (σ*), thus stabilizing the axial conformer. explanation O lone pair to C-X !* orbital X .
Load more

Recommended publications
  • Retention Indices for Frequently Reported Compounds of Plant Essential Oils
    Retention Indices for Frequently Reported Compounds of Plant Essential Oils V. I. Babushok,a) P. J. Linstrom, and I. G. Zenkevichb) National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA (Received 1 August 2011; accepted 27 September 2011; published online 29 November 2011) Gas chromatographic retention indices were evaluated for 505 frequently reported plant essential oil components using a large retention index database. Retention data are presented for three types of commonly used stationary phases: dimethyl silicone (nonpolar), dimethyl sili- cone with 5% phenyl groups (slightly polar), and polyethylene glycol (polar) stationary phases. The evaluations are based on the treatment of multiple measurements with the number of data records ranging from about 5 to 800 per compound. Data analysis was limited to temperature programmed conditions. The data reported include the average and median values of retention index with standard deviations and confidence intervals. VC 2011 by the U.S. Secretary of Commerce on behalf of the United States. All rights reserved. [doi:10.1063/1.3653552] Key words: essential oils; gas chromatography; Kova´ts indices; linear indices; retention indices; identification; flavor; olfaction. CONTENTS 1. Introduction The practical applications of plant essential oils are very 1. Introduction................................ 1 diverse. They are used for the production of food, drugs, per- fumes, aromatherapy, and many other applications.1–4 The 2. Retention Indices ........................... 2 need for identification of essential oil components ranges 3. Retention Data Presentation and Discussion . 2 from product quality control to basic research. The identifi- 4. Summary.................................. 45 cation of unknown compounds remains a complex problem, in spite of great progress made in analytical techniques over 5.
    [Show full text]
  • Zn-Nx Sites on N-Doped Carbon for Aerobic Oxidative Cleavage
    ARTICLE https://doi.org/10.1038/s41467-021-25118-0 OPEN Zn-Nx sites on N-doped carbon for aerobic oxidative cleavage and esterification of C(CO)-C bonds ✉ ✉ Chao Xie1, Longfei Lin 2, Liang Huang 3, Zixin Wang1, Zhiwei Jiang 1, Zehui Zhang1 & Buxing Han 2 Selective cleavage of C-C bonds is very important in organic chemistry, but remains chal- lenging because of their inert chemical nature. Herein, we report that Zn/NC-X catalysts, in 1234567890():,; which Zn2+ coordinate with N species on microporous N-doped carbon (NC) and X denotes the pyrolysis temperature, can effectively catalyze aerobic oxidative cleavage of C(CO)-C bonds and quantitatively convert acetophenone to methyl benzoate with a yield of 99% at 100 °C. The Zn/NC-950 can be applied for a wide scope of acetophenone derivatives as well as more challenging alkyl ketones. Detail mechanistic investigations reveal that the catalytic performance of Zn/NC-950 can be attributed to the coordination between Zn2+ and N species to change the electronic state of the metal, synergetic effect of the Zn single sites with their surrounding N atoms, as well as the microporous structure with the high surface area and structural defects of the NC. 1 Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education & Hubei Key Laboratory of Catalysis and Materials Science, South- Central University for Nationalities, Wuhan, China. 2 Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China. 3 The State Key Laboratory of Refractories and Metallurgy, ✉ Wuhan University of Science and Technology, Wuhan, China.
    [Show full text]
  • Working with Hazardous Chemicals
    A Publication of Reliable Methods for the Preparation of Organic Compounds Working with Hazardous Chemicals The procedures in Organic Syntheses are intended for use only by persons with proper training in experimental organic chemistry. All hazardous materials should be handled using the standard procedures for work with chemicals described in references such as "Prudent Practices in the Laboratory" (The National Academies Press, Washington, D.C., 2011; the full text can be accessed free of charge at http://www.nap.edu/catalog.php?record_id=12654). All chemical waste should be disposed of in accordance with local regulations. For general guidelines for the management of chemical waste, see Chapter 8 of Prudent Practices. In some articles in Organic Syntheses, chemical-specific hazards are highlighted in red “Caution Notes” within a procedure. It is important to recognize that the absence of a caution note does not imply that no significant hazards are associated with the chemicals involved in that procedure. Prior to performing a reaction, a thorough risk assessment should be carried out that includes a review of the potential hazards associated with each chemical and experimental operation on the scale that is planned for the procedure. Guidelines for carrying out a risk assessment and for analyzing the hazards associated with chemicals can be found in Chapter 4 of Prudent Practices. The procedures described in Organic Syntheses are provided as published and are conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board of Directors do not warrant or guarantee the safety of individuals using these procedures and hereby disclaim any liability for any injuries or damages claimed to have resulted from or related in any way to the procedures herein.
    [Show full text]
  • Covalent Bonding - Benzoic Acid from Ethyl Benzoate by Base Hydrolysis C1031 Expt 2
    Covalent Bonding - Benzoic Acid from Ethyl Benzoate by Base Hydrolysis C1031 Expt 2 EXPERIMENT 2: Covalent Bonding - Benzoic Acid from Ethyl Benzoate by Base Hydrolysis Introduction Ethyl benzoate (boiling point 211-213°C, melting point -34°C) belongs to a class of compounds called esters. It is a sweet smelling, colourless, liquid used in perfumery under the name Essence de Niobe; in the manufacture of Peau d’Espagne; and as an artificial fruit essence. It is soluble in organic solvents but insoluble in water. When ethyl benzoate is shaken with water two liquid layers form. The upper layer is ethyl benzoate (less dense) and the lower layer is water. There is no clear indication of any reaction taking place. A more careful study shows that ethyl benzoate reacts very slowly with water and is hydrolyzed1 to give benzoic acid and ethanol but the reaction does not go to completion. However, ethyl benzoate is found to react much faster with aqueous sodium hydroxide, the reaction going to completion, to give sodium benzoate (water soluble) and ethanol (miscible with water). - + O O CH2 CH3 O O Na (aq) C C + NaOH(aq) + CH3 CH2 OH Reaction 1 ethyl benzoate aqueous sodium hydroxide sodium benzoate ethanol (C9H10O2) (C7H5O2Na) This process is called base hydrolysis (or saponification) of an ester and is used in this experiment to first obtain sodium benzoate solution, and then benzoic acid from ethyl benzoate. The ethanol may be recovered by simple downward distillation from the reaction mixture and collected as a solution in water. But this step is omitted in this experiment to allow it to be completed in the available time.
    [Show full text]
  • Effect of Reaction Time on Base Hydrolysis of Methyl Benzoate
    EFFECT OF REACTION TIME ON BASE HYDROLYSIS OF METHYL BENZOATE ROSSIDAH SINJAANAK DAVID DARI (43864) Bachelor ofScience with Honours (Resource Chemistry) 2016 EFFECT OF REACTIONN TIME ON BASE HYDROLYSIS OF METHYL BENZOATE ROSSIDAH SINJA ANAK DAVID DARI (43864) This project paper is submitted in partial fulfillment of requirements the Degree of Bachelor of Science with honors (Program of Resource Chemistry) Faculty of Resource Science and Technology UNIVERSITI MALAYSIA SARAWAK 2016 II ,...... 7 r Acknowledgement I would like to express my deepest gratitude to the many people that helped to bring this research project to success. I want to thank, first and foremost my supervisor, Miss Yusralina bt Yusof for providing me the opportunity to taking part in this Final Year Project. I am so grateful for her help, professionalism and valuable guidance throughout this project that I do not have enough words to give my sincere appreciation. I would also like to thank all the staffs that involve in the analysis of data for this research project. Without their passionate participation and input, the analysis of data could not have successfully conducted. I am indebted to my friends who support me in this research project through the entire year. I cannot find words to express my gratitude to them in making this research project to fruition. I consider it an honor to work with all of them during this project. Last but not least, I must express my profound gratitude to my parents for providing me with unfailing support throughout my years of study and through the process of researching and writing this thesis.
    [Show full text]
  • Recommended Methods for the Identification and Analysis of Cocaine in Seized Materials
    Recommended methods for the Identification and Analysis of Cocaine in Seized Materials MANUAL FOR USE BY NATIONAL DRUG ANALYSIS LABORATORIES Photo credits: UNODC Photo Library; UNODC/Ioulia Kondratovitch; Alessandro Scotti. Laboratory and Scientific Section UNITED NATIONS OFFICE ON DRUGS AND CRIME Vienna Recommended Methods for the Identification and Analysis of Cocaine in Seized Materials (Revised and updated) MANUAL FOR USE BY NATIONAL DRUG ANALYSIS LABORATORIES UNITED NATIONS New York, 2012 Note Operating and experimental conditions are reproduced from the original reference materials, including unpublished methods, validated and used in selected national laboratories as per the list of references. A number of alternative conditions and substitution of named commercial products may provide comparable results in many cases, but any modification has to be validated before it is integrated into laboratory routines. Mention of names of firms and commercial products does not imply the endorse- ment of the United Nations. ST/NAR/7/REV.1 Original language: English © United Nations, March 2012. All rights reserved. The designations employed and the presentation of material in this publication do not imply the expression of any opinion whatsoever on the part of the Secretariat of the United Nations concerning the legal status of any country, territory, city or area, or of its authorities, or concerning the delimitation of its frontiers or boundaries. This publication has not been formally edited. Publishing production: English, Publishing and Library Section, United Nations Office at Vienna. ii Contents Page 1. Introduction ................................................. 1 1.1 Background .............................................. 1 1.2 Purpose and use of the manual .............................. 1 2. Physical appearance and chemical characteristics of coca leaf and illicit materials containing cocaine ................................
    [Show full text]
  • 045 of the Ethyl Ether of ?It;;, Yellow Monoclinic Prisms, Showing a Great Tentleiicy to Form Twins and Twin Clusters
    I'KEPAKA'I'ION 01.' ES'I'GKS BY KEPLi\CEBIEXT OP BLKOXYL. 045 of the ethyl ether of ?it;;, yellow monoclinic prisms, showing a great tentleiicy to form twins and twin clusters. If any condensation product (m.p., 216') is formed it may be removed by dissolving the ethoxy com- pound in ether. The pure ether melts at 133". '1 he crystals of this ether were examined by Mr. Walter B. Jones of the Geology Department and his report is as follows : photomicrograph X-l!; ocular, 2; objective, 3; arc light; exposure 3 seconds through blue &i\s and through 12 mm. of solution. Triclinic system, tabular habit; lxiul, macro and brachy pinacoids, usually modified by unit prism, 1na~~10:rnd hrachy domes. Inclination of angle, --So * . Subs, 0.3872. AgCl, 0.8013. Calc. for CIOHIIO~N&!I~:C1, 33.80. Found 33.70 Ethers of the Higher Alcohols.--So ethers could be made with n- prop?*1,u-butyl and iso-amyl alcohols although both methods of prepara- tion were tried a number of times, and inodifications of these methods were rcwrted to. Summary. hen ethers are obtained by the action of alcohols upon the addition products of chloral and wazefa- or prim-nitro-aniline. The vi-nitro-aniline product gave ethers with methyl, ethyl, wpropyl, n-butyl and iso-amyl alcohols. The p-nitro-aniline product gaye ethers only with methyl and ethyl alcohols. In these cases the amine was made to react with the chloral alcoholate. No ethers of the higher alcohols could be obtained. ('l14PT:L HILL,N.
    [Show full text]
  • Experiment 5 Carboxylic Acids and Saponification of Methyl Benzoate
    Experiment 5 Carboxylic Acids and Saponification of Methyl Benzoate In the first part of this experiment you are going to evaluate the solubility of salicylic acid in water, hot water and in the presence of aqueous NaOH. As you would expect carboxylic acids should react with water to form a water soluble carboxylate anion but solubility is also dependent of the size of the alkyl or aryl group attached to the carboxylic acid functional group. In general the following acid-base reaction occurs: - + R-COOH + H2O RCOO (aq) + H3O (aq) The structure for salicylic acid is given below: OH C OH O Salicylic acid Additionally, carboxylic acids react with bases to form water soluble salts as shown below: - + R-COOH + NaOH (aq) RCOO Na (aq) + H2O Note that salicylic acid contains, in addition to the carboxylic acid functional group, a phenol group hydrogen that can also be titrated by base. The resultant sodium carboxylate/phenolate salt can further react with acids to reform the free acid (COOH) and phenol (Ph-OH) as shown below: R-COO-Na+ (aq) + HCl (aq) RCOOH + NaCl (aq) Ph-O-Na+ (aq) + HCl (aq) Ph-OH + NaCl (aq) The use of bases and acids serves as solubility switches to convert an insoluble form of a compound to a soluble form and vice versa. Observing the solubility or insolubility of reactants and/or products serves as a means to monitor acid base reactions. The concept of a solubility switch will also serve as the basis for following the base (NaOH) catalyzed hydrolysis (saponification) reaction of an ester (methyl benzoate) to the subsequent water soluble carboxylate salt (sodium benzoate) and alcohol (methanol).
    [Show full text]
  • Methyl Benzoate
    CHM230 - Preparation of Methyl Benzoate Preparation of Methyl Benzoate Introduction The ester group is an important functional group that can be synthesized in a number of different ways. The low-molecular-weight esters have very pleasant odors and indeed are the major components of the flavor and odor aspects of a number of fruits. Although the natural flavor may contain nearly a hundred different compounds, single esters approximate the natural odors and are often used in the food industry for artificial flavors and fragrances. Esters can be prepared by the reaction of a carboxylic acid with an alcohol in the presence of a catalyst such as concentrated sulfuric acid, hydrogen chloride, p-toluenesulfonic acid, or the acid form of an ion exchange resin: This Fischer esterification reaction reaches equilibrium after a few hours of refluxing. The position of the equilibrium can be shifted by adding more of the acid or of the alcohol, depending on cost or availability. The mechanism of the reaction involves initial protonation of the carboxyl group, attack by the nucleophilic hydroxyl, a proton transfer, and loss of water followed by loss of the catalyzing proton to give the ester. In this experiment you will prepare methyl benzoate by reacting benzoic acid with methanol using sulfuric acid as a catalyst. Since this is a reversible reaction, it will reach an equilibrium that is described by the equilibrium constant, Keq . For this experiment, you will isolate the product, methyl benzoate, and any unreacted benzoic acid. Using this data, you will calculate the equilibrium constant for the reaction (see calculation section below).
    [Show full text]
  • Dielectric Constant Chart
    Dielectric Constants of Common Materials DIELECTRIC MATERIALS DEG. F CONSTANT ABS RESIN, LUMP 2.4-4.1 ABS RESIN, PELLET 1.5-2.5 ACENAPHTHENE 70 3 ACETAL 70 3.6 ACETAL BROMIDE 16.5 ACETAL DOXIME 68 3.4 ACETALDEHYDE 41 21.8 ACETAMIDE 68 4 ACETAMIDE 180 59 ACETAMIDE 41 ACETANILIDE 71 2.9 ACETIC ACID 68 6.2 ACETIC ACID (36 DEGREES F) 36 4.1 ACETIC ANHYDRIDE 66 21 ACETONE 77 20.7 ACETONE 127 17.7 ACETONE 32 1.0159 ACETONITRILE 70 37.5 ACETOPHENONE 75 17.3 ACETOXIME 24 3 ACETYL ACETONE 68 23.1 ACETYL BROMIDE 68 16.5 ACETYL CHLORIDE 68 15.8 ACETYLE ACETONE 68 25 ACETYLENE 32 1.0217 ACETYLMETHYL HEXYL KETONE 66 27.9 ACRYLIC RESIN 2.7 - 4.5 ACTEAL 21 3.6 ACTETAMIDE 4 AIR 1 AIR (DRY) 68 1.000536 ALCOHOL, INDUSTRIAL 16-31 ALKYD RESIN 3.5-5 ALLYL ALCOHOL 58 22 ALLYL BROMIDE 66 7 ALLYL CHLORIDE 68 8.2 ALLYL IODIDE 66 6.1 ALLYL ISOTHIOCYANATE 64 17.2 ALLYL RESIN (CAST) 3.6 - 4.5 ALUMINA 9.3-11.5 ALUMINA 4.5 ALUMINA CHINA 3.1-3.9 ALUMINUM BROMIDE 212 3.4 ALUMINUM FLUORIDE 2.2 ALUMINUM HYDROXIDE 2.2 ALUMINUM OLEATE 68 2.4 1 Dielectric Constants of Common Materials DIELECTRIC MATERIALS DEG. F CONSTANT ALUMINUM PHOSPHATE 6 ALUMINUM POWDER 1.6-1.8 AMBER 2.8-2.9 AMINOALKYD RESIN 3.9-4.2 AMMONIA -74 25 AMMONIA -30 22 AMMONIA 40 18.9 AMMONIA 69 16.5 AMMONIA (GAS?) 32 1.0072 AMMONIUM BROMIDE 7.2 AMMONIUM CHLORIDE 7 AMYL ACETATE 68 5 AMYL ALCOHOL -180 35.5 AMYL ALCOHOL 68 15.8 AMYL ALCOHOL 140 11.2 AMYL BENZOATE 68 5.1 AMYL BROMIDE 50 6.3 AMYL CHLORIDE 52 6.6 AMYL ETHER 60 3.1 AMYL FORMATE 66 5.7 AMYL IODIDE 62 6.9 AMYL NITRATE 62 9.1 AMYL THIOCYANATE 68 17.4 AMYLAMINE 72 4.6 AMYLENE 70 2 AMYLENE BROMIDE 58 5.6 AMYLENETETRARARBOXYLATE 66 4.4 AMYLMERCAPTAN 68 4.7 ANILINE 32 7.8 ANILINE 68 7.3 ANILINE 212 5.5 ANILINE FORMALDEHYDE RESIN 3.5 - 3.6 ANILINE RESIN 3.4-3.8 ANISALDEHYDE 68 15.8 ANISALDOXINE 145 9.2 ANISOLE 68 4.3 ANITMONY TRICHLORIDE 5.3 ANTIMONY PENTACHLORIDE 68 3.2 ANTIMONY TRIBROMIDE 212 20.9 ANTIMONY TRICHLORIDE 166 33 ANTIMONY TRICHLORIDE 5.3 ANTIMONY TRICODIDE 347 13.9 APATITE 7.4 2 Dielectric Constants of Common Materials DIELECTRIC MATERIALS DEG.
    [Show full text]
  • Supporting Information
    Supporting information Oxidative cleavage of α-arylaldehydes using iodosylbenzene Nizam Havare and Dietmar A. Plattner S1 General: All used substrate were prepared following published procedures [a-m]. Starting materials: (diacetoxyiodo)benzene, Dess-Martin reagent, 2-(4-nitrophenyl)ethanol, 2-(4- chlorophenyl)ethanol, phenylacetaldehyde, 2-(2-naphthyl)ethanol, 2-(4-methoxy)ethanol, 2- methoxy-2-phenylethanol, 2-phenylpropanal, 2-phenyl-1-butanol, cyclohexyl- phenylacetonitrile, α-tetralone, 2-acetylnaphthalene, anethol, 4-nitroacetophenone and solvents were obtained commercially from ABCR , Sigma-Aldrich , Fluka , Alfa Aesar and Acros. Dichloromethane was dried over potassium carbonate, freshly distilled and stored under Ar prior to use. Cyclohexane was dried over sodium, freshly distilled and stored under Ar prior to use. Ethyl acetate was dried over phosphor pentaoxide, freshly distilled and stored under Ar prior to use. Column chromatography: Silica gel 60 : 0.06-0.2 mm, Carl Roth GmbH. 1 TLC: Silica gel 60 F 254 25 Aluminium sheets 20x20 cm from Merck KGaA co. Darmstadt. H- spectra: Varian 300 and Bruker 500 spectrometer. GC-MS: (GC Varian 3400 , achiral GC column Macherey-Nagel optima 5 MS 30 m x0.25 mmØ, 0.25 µm film). MS: Thermo TSQ 700. Preparation of CO detection reagent (PdCl 2/HCl): 100 ml of water is added to 130 mg of palladium(II)chloride (0.733 mmol, 99.7%) in a 250 ml volumetric flask. 1 ml of HCl solution is added, which was prepared from mixture of conc. HCl/water (V/V = 1:10). The suspension is stirred for one day at room temperature, until giving a clear solution.
    [Show full text]
  • United States Patent [191 [11] 3,943,181 Fleischer Et Al
    United States Patent [191 [11] 3,943,181 Fleischer et al. , [45] Mar. 9, 1976 [54] SEPARATING OPTICALLY PURE d- AND 397,212 8/1933 United Kingdom ........... .. 260/631 R l-ISOMERS 0F MENTHOL, NEOMENTHOL AND ISOMENTHOL " OTHER PUBLICATIONS [75] Inventors: Jiirgen Fleischer, Cologne; Kurt Gilman Ed., Organic Chemistry, Wiley, N.Y., 1943, p. Bauer; Ruldolf Hopp, both of 254. Holzminden, all of Germany Reed et al_, J. Chem. Soc., pp. 167-173 (1933). [73] Assignee: Haarmann & Reimer Gesellschaft mit beschrankter Haftung Primary Examiner-Be1‘nard l-lel?n Assistant Examiner-James H. Reamer [22] Filed: Sept. 3, 1974 Attorney, Agent, or Firm—Burgess, Dinklage & [21] Appl. No.: 503,004 Sprung Related US. Application Data [63] Continuation of Ser. No. 229,109, Feb. 24, 1972, [57] ABSTRACT ' abandoned. A process for the separation of optically active d— and [30] Foreign Application Priority Data l-isomers of a compound selected from the group con sisting of menthol, neomenthol and isomenthol, which Feb. 27, 1971 Germany .......................... .. 2109456 comprises esterifying a d,l-isomeric mixture of the Feb. 2, 1972 Germany .......................... .. 2204771 compound with an acid selected from the group con sisting of benzoic acid optionally carrying at least one [52] US. Cl...... 260/631 R; 260/473 R; 260/471 R; substituent on the benzene ring and hexahydrobenzoic 260/468 R; 260/476 R acid; forming a supersaturated solution or a super [51] Int. Cl.2 ........................................ .. C07C 35/12 cooled melt of the dJ-ester; inoculating the solution or [58] Field of Search ................... .. 260/631 R, 631 H melt with crystals of the d- or l-form of the ester to effect selective crystallization of one of the two [56] References Cited optical isomers; separating the crystals and subjecting UNITED STATES PATENTS them to hydrolysis to yield the corresponding enantio 2,120,131 6/1938 Harris ..........................
    [Show full text]