Chapter 6 Amines and Amides
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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. -
Aldehydes and Ketones Are Simple Organic Compounds Containing a Carbonyl Group
Aldehydes and Ketones are simple organic compounds containing a carbonyl group. Carbonyl group contains carbon- oxygen double bond. These organic compounds are simple because the carbon atom presents in the carbonyl group lack reactive groups such as OH or Cl. By Dr. Sayed Hasan Mehdi Assistant Professor Department of Chemistry Shia P.G. College, Lucknow Dr. S.Hasan Mehdi 6/13/2020 This is to bring to kind notice that the matter of this e- content is for the B.Sc. IV semester students. It has been taken from the following sources. The students are advised to follow these books as well. •A TEXTBOOK OF ORGANIC CHEMISTRY by Arun Bahl & B.S. Bahl, S. Chand & Company Ltd. Publication. •Graduate Organic Chemistry by M. K. Jain and S.C. Sharma, Vishal Publishing Co. •Pradeep’s Organic Chemistry Vol II by R. N. Dhawan, Pradeep Publication, Jalandhar. Dr. S.Hasan Mehdi 6/13/2020 An aldehyde is one of the classes of carbonyl group- containing alkyl group on one end and hydrogen on the other end. The R and Ar denote alkyl or aryl member respectively. In the condensed form, the aldehyde is written as –CHO. Dr. S.Hasan Mehdi 6/13/2020 Dr. S.Hasan Mehdi 6/13/2020 1. From Alcohols: a. By oxidation of Alcohols: Aldehydes and ketones can be prepared by the controlled oxidation of primary and secondary alcohols using an acidified solution of potassium dichromate or permanganate. Primary alcohol produces aldehydesRef. Last slide. O K Cr O RCH2OH + [O] 2 2 7 + R C H H 10 Alcohol Aldehyde O CH3CH2OH+ [O] K2Cr2O7 + CH3 C H H Ethyl Alcohol Acetaldehyde The aldehydes formed in the above reaction are very easily oxidised to carboxylc acids if allowed to remain in the reaction mixture. -
Acetal (POM) Chemical Compatibility Chart From
ver 31-Mar-2020 Acetal (POM) Chemical Compatibility Chart Chemical Chemical Acetaldehyde A Ammonium Acetate C Acetamide A Ammonium Bifluoride D Acetate Solvents A Ammonium Carbonate D Acetic Acid D Ammonium Caseinate D Acetic Acid, 20% C Ammonium Chloride, 10% B Acetic Acid, 80% D Ammonium Hydroxide D Acetic Acid, Glacial D Ammonium Nitrate, 10% A Acetic Anhydride D Ammonium Oxalate B Acetone A Ammonium Persulfate D Acetyl Chloride, dry D Ammonium Phosphate, Dibasic B Acetylene A Ammonium Phosphate, Monobasic B Alcohols: Amyl A Ammonium Phosphate, Tribasic B Alcohols: Benzyl A Ammonium Sulfate B Alcohols: Butyl A Ammonium Sulfite D Alcohols: Diacetone A Ammonium Thiosulfate B Alcohols: Ethyl A Amyl Acetate B Alcohols: Hexyl A Amyl Alcohol A Alcohols: Isobutyl A Amyl Chloride A Alcohols: Isopropyl A Aniline A Alcohols: Methyl A Aniline Oil D Alcohols: Octyl A Anise Oil D Alcohols: Propyl (1-Propanol) A Antifreeze D Aluminum chloride, 20% C Aqua Regia (80% HCl, 20% HNO3) D Aluminum Fluoride C Aromatic Hydrocarbons A Aluminum Hydroxide A Arsenic Acid D Aluminum Nitrate B Asphalt B Aluminum Potassium Sulfate, 10% C Barium Carbonate A Aluminum Potassium Sulfate, 100% C Barium Chloride A Aluminum Sulfate, 10% B Barium Cyanide B Alums C Barium Hydroxide D Amines D Barium Nitrate B Ammonia, 10% (Ammonium Hydroxide) C Barium Sulfate B Ammonia, 10% D Barium Sulfide A Ammonia, anhydrous D Bay Oil D Ammonia, liquid D Beer A Ammonia Nitrate C Beet Sugar Liquids B Key to General Chemical Resistance – All data is based on ambient or room temperature conditions, about 64°F (18°C) to 73°F (23°C) A = Excellent C = Fair - Moderate Effect, not recommended B= Good - Minor Effect, slight corrosion or discoloration D = Severe Effect, not recommended for ANY use It is the sole responsibility of the system designer and user to select products suitable for their specific application requirements and to ensure proper installation, operation, and maintenance of these products. -
The Relative Rates of Thiol–Thioester Exchange and Hydrolysis for Alkyl and Aryl Thioalkanoates in Water
Orig Life Evol Biosph (2011) 41:399–412 DOI 10.1007/s11084-011-9243-4 PREBIOTIC CHEMISTRY The Relative Rates of Thiol–Thioester Exchange and Hydrolysis for Alkyl and Aryl Thioalkanoates in Water Paul J. Bracher & Phillip W. Snyder & Brooks R. Bohall & George M. Whitesides Received: 14 April 2011 /Accepted: 16 June 2011 / Published online: 5 July 2011 # Springer Science+Business Media B.V. 2011 Abstract This article reports rate constants for thiol–thioester exchange (kex), and for acid- mediated (ka), base-mediated (kb), and pH-independent (kw) hydrolysis of S-methyl thioacetate and S-phenyl 5-dimethylamino-5-oxo-thiopentanoate—model alkyl and aryl thioalkanoates, respectively—in water. Reactions such as thiol–thioester exchange or aminolysis could have generated molecular complexity on early Earth, but for thioesters to have played important roles in the origin of life, constructive reactions would have needed to compete effectively with hydrolysis under prebiotic conditions. Knowledge of the kinetics of competition between exchange and hydrolysis is also useful in the optimization of systems where exchange is used in applications such as self-assembly or reversible binding. For the alkyl thioester S-methyl thioacetate, which has been synthesized in −5 −1 −1 −1 −1 −1 simulated prebiotic hydrothermal vents, ka = 1.5×10 M s , kb = 1.6×10 M s , and −8 −1 kw = 3.6×10 s . At pH 7 and 23°C, the half-life for hydrolysis is 155 days. The second- order rate constant for thiol–thioester exchange between S-methyl thioacetate and 2- −1 −1 sulfonatoethanethiolate is kex = 1.7 M s . -
Chapter 7, Haloalkanes, Properties and Substitution Reactions of Haloalkanes Table of Contents 1
Chapter 7, Haloalkanes, Properties and Substitution Reactions of Haloalkanes Table of Contents 1. Alkyl Halides (Haloalkane) 2. Nucleophilic Substitution Reactions (SNX, X=1 or 2) 3. Nucleophiles (Acid-Base Chemistry, pka) 4. Leaving Groups (Acid-Base Chemistry, pka) 5. Kinetics of a Nucleophilic Substitution Reaction: An SN2 Reaction 6. A Mechanism for the SN2 Reaction 7. The Stereochemistry of SN2 Reactions 8. A Mechanism for the SN1 Reaction 9. Carbocations, SN1, E1 10. Stereochemistry of SN1 Reactions 11. Factors Affecting the Rates of SN1 and SN2 Reactions 12. --Eliminations, E1 and E2 13. E2 and E1 mechanisms and product predictions In this chapter we will consider: What groups can be replaced (i.e., substituted) or eliminated The various mechanisms by which such processes occur The conditions that can promote such reactions Alkyl Halides (Haloalkane) An alkyl halide has a halogen atom bonded to an sp3-hybridized (tetrahedral) carbon atom The carbon–chlorine and carbon– bromine bonds are polarized because the halogen is more electronegative than carbon The carbon-iodine bond do not have a per- manent dipole, the bond is easily polarizable Iodine is a good leaving group due to its polarizability, i.e. its ability to stabilize a charge due to its large atomic size Generally, a carbon-halogen bond is polar with a partial positive () charge on the carbon and partial negative () charge on the halogen C X X = Cl, Br, I Different Types of Organic Halides Alkyl halides (haloalkanes) sp3-hybridized Attached to Attached to Attached -
Esters Introduction Structurally, an Ester Is a Compound That Has an Alkoxy (OR) Group Attached to the Carbonyl Group
Esters Introduction Structurally, an ester is a compound that has an alkoxy (OR) group attached to the carbonyl group. O R C O R' R may be H, alkyl or aryl, while R’ may be alkyl or aryl only. Esters are widespread in nature. Many of the fragrances of flowers and fruits are due to the esters present. Ethyl butanoate is the chief component that accounts for the pineapple-like aroma and flavour of pineapples. 1:18 PM 1 Nomenclature of Esters Names of esters consist of two words that reflect the composite structure of the ester. The first word is derived from the alkyl group of the alcohol component, and the second word from the carboxylate group of the carboxylic acid component of the ester. The name of the carboxylate portion is derived by substituting the -ic acid suffix of the parent carboxylic acid with the –ate suffix. The alkyl group is cited first followed by the carboxylate group separated by a space. An ester is thus named as an alkyl 1:18 PM alkanoate. 2 IUPAC Nomenclature of Esters Examples 1:18 PM 3 Synthesis of Esters Preparative Strategies Highlighted below are some of the most common strategies by which esters are prepared. The esters are commonly prepared from the reaction of carboxylic acids, acid chlorides and acid anhydrides with alcohols. 1:18 PM 4 Synthesis of Esters Acid-Catalysed Esterification of a Carboxylic Acid and an Alcohol The acid-catalysed reaction of carboxylic acids and alcohols provides esters. Typically, a catalytic amount of a strong inorganic (mineral) acid such as H2SO4, HCl and H3PO4 is used. -
INDOLES from 2-METHYLNITROBENZENES by CONDENSATION with FORMAMIDE ACETALS FOLLOWED by REDUCTION: 4-BENZYLOXYINDOLE [1H-Indole, 4-(Phenylmethoxy)-]
DOI:10.15227/orgsyn.063.0214 Organic Syntheses, Coll. Vol. 7, p.34 (1990); Vol. 63, p.214 (1985). INDOLES FROM 2-METHYLNITROBENZENES BY CONDENSATION WITH FORMAMIDE ACETALS FOLLOWED BY REDUCTION: 4-BENZYLOXYINDOLE [1H-Indole, 4-(phenylmethoxy)-] Submitted by Andrew D. Batcho1 and Willy Leimgruber2. Checked by David J. Wustrow and Andrew S. Kende. 1. Procedure A. 6-Benzyloxy-2-nitrotoluene. A stirred mixture of 124.7 g (0.81 mol) of 2-methyl-3-nitrophenol (Note 1), 113.2 g (0.90 mol) of benzyl chloride, 112.2 g (0.81 mol) of anhydrous potassium carbonate, and 800 mL of dimethylformamide (DMF) is heated at 90°C for 3 hr. Most of the DMF is removed on a rotary evaporator (20 mm) and the oily residue is poured into 400 mL of 1 N sodium hydroxide and extracted with ether (3 × 800 mL). The combined extracts are dried (Na2SO4), filtered, and evaporated to give 203.5 g of yellowish solid. Recrystallization from 1 L of methanol cooled to 0°C affords 177.6 (90%) of 6-benzyloxy-2-nitrotoluene as pale-yellow crystals, mp 61–63°C3 (Note 2). B. (E)-6-Benzyloxy-2-nitro-β-pyrrolidinostyrene. To a solution of 175.4 g (0.72 mol) of 6- benzyloxy-2-nitrotoluene in 400 mL of DMF are added 102.5 g (0.84 mol) of N,N-dimethylformamide dimethyl acetal (Note 3) and 59.8 g (0.84 mol) of pyrrolidine. The solution is heated at reflux (110°C) for 3 hr (Note 4) under nitrogen and allowed to cool to room temperature. -
Fermentation and Ester Taints
Fermentation and Ester Taints Anita Oberholster Introduction: Aroma Compounds • Grape‐derived –provide varietal distinction • Yeast and fermentation‐derived – Esters – Higher alcohols – Carbonyls – Volatile acids – Volatile phenols – Sulfur compounds What is and Esters? • Volatile molecule • Characteristic fruity and floral aromas • Esters are formed when an alcohol and acid react with each other • Few esters formed in grapes • Esters in wine ‐ two origins: – Enzymatic esterification during fermentation – Chemical esterification during long‐term storage Ester Formation • Esters can by formed enzymatically by both the plant and microbes • Microbes – Yeast (Non‐Saccharomyces and Saccharomyces yeast) – Lactic acid bacteria – Acetic acid bacteria • But mainly produced by yeast (through lipid and acetyl‐CoA metabolism) Ester Formation Alcohol function Keto acid‐Coenzyme A Ester Ester Classes • Two main groups – Ethyl esters – Acetate esters • Ethyl esters = EtOH + acid • Acetate esters = acetate (derivative of acetic acid) + EtOH or complex alcohol from amino acid metabolism Ester Classes • Acetate esters – Ethyl acetate (solvent‐like aroma) – Isoamyl acetate (banana aroma) – Isobutyl acetate (fruit aroma) – Phenyl ethyl acetate (roses, honey) • Ethyl esters – Ethyl hexanoate (aniseed, apple‐like) – Ethyl octanoate (sour apple aroma) Acetate Ester Formation • 2 Main factors influence acetate ester formation – Concentration of two substrates acetyl‐CoA and fusel alcohol – Activity of enzyme responsible for formation and break down reactions • Enzyme activity influenced by fermentation variables – Yeast – Composition of fermentation medium – Fermentation conditions Acetate/Ethyl Ester Formation – Fermentation composition and conditions • Total sugar content and optimal N2 amount pos. influence • Amount of unsaturated fatty acids and O2 neg. influence • Ethyl ester formation – 1 Main factor • Conc. of precursors – Enzyme activity smaller role • Higher fermentation temp formation • C and N increase small effect Saerens et al. -
Chapter 14 – Aldehydes and Ketones
Chapter 14 – Aldehydes and Ketones 14.1 Structures and Physical Properties of Aldehydes and Ketones Ketones and aldehydes are related in that they each possess a C=O (carbonyl) group. They differ in that the carbonyl carbon in ketones is bound to two carbon atoms (RCOR’), while that in aldehydes is bound to at least one hydrogen (H2CO and RCHO). Thus aldehydes always place the carbonyl group on a terminal (end) carbon, while the carbonyl group in ketones is always internal. Some common examples include (common name in parentheses): O O H HH methanal (formaldehyde) trans-3-phenyl-2-propenal (cinnamaldehyde) preservative oil of cinnamon O O propanone (acetone) 3-methylcyclopentadecanone (muscone) nail polish remover a component of one type of musk oil Simple aldehydes (e.g. formaldehyde) typically have an unpleasant, irritating odor. Aldehydes adjacent to a string of double bonds (e.g. 3-phenyl-2-propenal) frequently have pleasant odors. Other examples include the primary flavoring agents in oil of bitter almond (Ph- CHO) and vanilla (C6H3(OH)(OCH3)(CHO)). As your book says, simple ketones have distinctive odors (similar to acetone) that are typically not unpleasant in low doses. Like aldehydes, placing a collection of double bonds adjacent to a ketone carbonyl generally makes the substance more fragrant. The primary flavoring agent in oil of caraway is just a such a ketone. 2 O oil of carraway Because the C=O group is polar, small aldehydes and ketones enjoy significant water solubility. They are also quite soluble in typical organic solvents. 14.2 Naming Aldehydes and Ketones Aldehydes The IUPAC names for aldehydes are obtained by using rules similar to those we’ve seen for other functional groups (e.g. -
Reduction of Organic Functional Groups Using Hypophosphites Rim Mouselmani
Reduction of Organic Functional Groups Using Hypophosphites Rim Mouselmani To cite this version: Rim Mouselmani. Reduction of Organic Functional Groups Using Hypophosphites. Other. Univer- sité de Lyon; École Doctorale des Sciences et de Technologie (Beyrouth), 2018. English. NNT : 2018LYSE1241. tel-02147583v2 HAL Id: tel-02147583 https://tel.archives-ouvertes.fr/tel-02147583v2 Submitted on 5 Jun 2019 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THESE de DOCTORAT DE L’UNIVERSITE DE LYON EN COTUTELLE AVEC L'UNIVERSITÉ LIBANAISE opérée au sein de l’Université Claude Bernard Lyon 1 École Doctorale de Chimie-École Doctorale des Sciences et Technologies Discipline : Chimie Soutenue publiquement le 07/11/2018, par Rim MOUSELMANI Reduction of Organic Functional Groups Using Hypophosphites Devant le jury composé de Mme. Micheline DRAYE Université Savoie Mont Blanc Rapporteure M. Mohammad ELDAKDOUKI Université Arabe de Beyrouth Rapporteur Mme. Emmanuelle SCHULZ Université Paris 11 examinatrice M. Abderrahmane AMGOUNE Université Lyon 1 Président M. Mahmoud FARAJ Université Internationale Libanaise examinateur Mme. Estelle MÉTAY Université Lyon 1 Directrice de thèse M. Ali HACHEM Université Libanaise Directeur de thèse M. Marc LEMAIRE Université Lyon 1 Membre invité M. -
Handout: Organic Chemistry Reactions
Handout: Organic Chemistry Reactions Reactions Organized by Compound Families Alkanes 1. Combustion 2. Halogenation Alkenes and Alkynes 1. Additions: hydrogenation, halogenation, hydrohalogenation, hydration 2. Polymerization Aromatic Compounds Substitutions: nitration, halogenation, sulfonation Alcohols 1. Elimination: dehydration 2. Oxidations Thiols Oxidation Amines Acid-Base reactions Aldehydes and Ketones 1. Addition: Acetal/hemiacetal formation by alcohol addition (Reverse rxn: Acetal hydrolysis with acid) 2. Oxidation and Reduction for aldehydes (*Ketones go through reduction only) Carboxylic Acids 1. Substitutions: esterification, amidation (Reverse rxns: ester hydrolysis with acid or base, amide hydrolysis with acid or base) 2. Acid-base reactions Phosphoric acid and Phosphates Phosphoric acid: Esterification with alcohol Phosphates: Phosphorylation H. Kim for Chem 30B 1 Reactions Organized by Reaction Type Family Reaction Example 1. ADDITION Alkenes and Hydrogenation H H Pd catalyst H H C C + H2 H C C H alkynes H H H H H H Pd catalyst H C C H + 2 H2 H C C H H H Halogenation H H Cl Cl C C + Cl2 (or Br2) H C C H H H H H H Cl Hydro- H H Markonikov’s Rule halogenation C C + HCl (or HBr) H C C H applies: H adds to C H CH3 H CH3 with more Hs already. H OH Hydration H H H+ catalyst C C + H2O H C C H Markonikov’s Rule H CH3 H CH3 applies. Aldehydes Addition of O OH H+ catalyst H3C C H(R) + CH3CH2OH and ketones alcohol to get H3C C H(R) + CH3CH2OH hemiacetals or O CH2CH3 acetals hemiacetal O CH2CH3 H+ catalyst H3C C H(R) + H2O O CH2CH3 acetal 2. -
Amide, and Paratoluenesulfonamide on the Amide of Silver,On the Imides
68 CHEMISTRY: E. C. FRANKLIN METALLIC SALTS OF AMMONO ACIDS By Edward C. Franklin DEPARTMENT OF CHEMISTRY, STANFORD UNIVERSITY Presented to the Academy, January 9. 1915 The Action of Liquid-Ammonia Solutions of Ammono Acids on Metallic Amides, Imides, and Nitrides. The acid amides and imides, and the metallic derivatives of the acid amides and imides are the acds, bases, and salts respectively of an ammonia system of acids, bases, and salts.1 Guided by the relationships implied in the above statement Franklin and Stafford were able to prepare potassium derivatives of a considerable number of acid amides by the action of potassium amide on certain acid amides in solution in liquid ammonia. That is to say, an ammono base, potassium amide, was found to react with ammono acids in liquid ammonia to form ammono salts just as the aquo base, potassium hydrox- ide, acts upon aquo acids in water solution to form aquo salts. Choos- ing, for example, benzamide and benzoic acid as representative acids of the two systems, the analogous reactions taking place respectively in liquid ammonia and water are represented by the equations: CH6CONH2+KNH2 = C6H5CONHK + NHs. CseHCONH2 + 2KNH2 = CIHsCONK2 + 2NH3. CH6tCOOH + KOH = CIH6COOK + H2O. The ammono acid, since it is dibasic, reacts with either one or two molecules of potassium amide to form an acid and a neutral salt. Having thus demonstrated the possibility of preparing ammono salts of potassium by the interaction of potassium amide and acid amides in liquid ammonia solution, it was further found that ammono salts of the heavy metals may be prepared by the action of liquid ammonia solutions of ammono acids on insoluble metallic amides, imides, and nitrides-that is, by reactions which are analogous to the formation of aquo salts in water by the action of potassium hydroxide on insoluble metallic hydroxides and oxides.