Chemistry
Reactions of Carboxylic Acids
Reactions of carboxylic acids involve various chemical transformations, including acid-base reactions, esterification, and decarboxylation. In acid-base reactions, carboxylic acids can donate a proton to a base. Esterification involves the formation of esters from carboxylic acids and alcohols, while decarboxylation results in the removal of a carboxyl group from the acid.
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10 Key excerpts on "Reactions of Carboxylic Acids"
eBook - PDF- Ramesh Chandra, Snigdha Singh, Aarushi Singh(Authors)
- 2019(Publication Date)
- Arcler Press(Publisher)
Carboxylic Acid Reactions and Uses 5 CONTENTS 5.1. Introduction .................................................................................... 166 5.2. Nomenclature Of Carboxylic Acids ................................................ 167 5.3. Carboxylic Acid Examples .............................................................. 167 5.4. Properties Of Carboxylic Acids ....................................................... 168 5.5. Physical Properties Of Carboxylic Acids ........................................ 169 5.6. The Acidity Of Carboxylic Acids .................................................... 171 5.7. Carboxylic Acid Derivatives And Acyl Groups ................................ 174 5.8. The Nucleophilic Acyl Substitution Reaction .................................. 177 5.9. The Relative Reactivity Of Carboxylic Acid Derivatives ................... 180 5.10. Uses Of Carboxylic Acids ............................................................. 184 References ............................................................................................. 195 Organic Reactions and their nomenclature 166 5.1. INTRODUCTION A carboxylic acid is an organic complex having a (COOH) carboxyl functional group. They come about broadly in nature and are also unnaturally manufactured by humans. Upon deprotonation (removal of a proton), carboxylic acids produce a carboxylate anion with the general formula R-COO–, which can give a variety of beneficial salts like soaps (Sáenz-Galindo et al., 2018). The most important functional group that present are the carboxylic acids C=O. This sort of organic compounds can be attained by different ways, some carboxylic acids, for example, fumaric acid, citric acid or lactic acid are formed from by fermentation most of these kinds of carboxylic acids are useful in the food industry (Oguz et al., 2017).
eBook - PDF- William H. Brown, Thomas Poon(Authors)
- 2017(Publication Date)
- Wiley(Publisher)
• The functional group of a carboxylic anhydride is two acyl groups bonded to an oxygen. • Symmetrical anhydrides are named by changing the suffix acid in the name of the parent carboxylic acid to anhydride. • The functional group of a carboxylic ester is an acyl group bonded to OR or OAr. • An ester is named by giving the name of the alkyl or aryl group bonded to oxygen first, followed by the name of the acid, in which the suffix ‐ic acid is replaced by the suffix ‐ate. • A cyclic ester is given the name lactone. • The functional group of an amide is an acyl group bonded to a trivalent nitrogen. • Amides are named by dropping the suffix ‐oic acid from the IUPAC name of the parent acid, or ‐ic acid from its common name, and adding ‐amide. • A cyclic amide is given the name lactam. 14.2 What Are the Characteristic Reactions of Carboxylic Acid Derivatives? • A common reaction theme of functional derivatives of car- boxylic acids is nucleophilic acyl addition to the carbonyl carbon to form a tetrahedral carbonyl addition intermedi- ate, which then collapses to regenerate the carbonyl group. The result is nucleophilic acyl substitution. 14.3 What Is Hydrolysis? • Hydrolysis is a chemical process whereby a bond (or bonds) in a molecule is broken by its reaction with water. • Hydrolysis of a carboxylic acid derivative results in a car- boxylic acid. 14.4 How Do Carboxylic Acid Derivatives React with Alcohols? • Carboxylic acid derivatives (except for amides) react with alcohols to give esters. • The reaction conditions required (i.e., neutral, acidic, or basic) depend on the type of derivative. 14.5 How Do Carboxylic Acid Derivatives React with Ammonia and Amines? • Carboxylic acid derivatives (except for amides) react with ammonia and amines to give amides.
eBook - PDF- Mark G. Moloney(Author)
- 2023(Publication Date)
- Wiley(Publisher)
43 2 Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and Their Derivatives C. T. Bedford Department of Chemistry, University College London, London WC1H 0AJ, UK CHAPTER MENU Intermolecular Catalysis and Reactions, 43 Carboxylic Acids and Their Derivatives, 43 (a) Esters, 43 (i) Transesterification, 43 (ii) Aminolysis Reactions, 45 Phosphoric Acids and Their Derivatives, 45 (a) Phosphates, 45 (b) Phosphinic Acids, 45 (c) Phosphoramidates, 46 Sulfonic Acids and Their Derivatives, 46 (a) Sulfinates, 46 Intramolecular Catalysis and Neighbouring Group Participation, 48 Biologically Significant Reactions, 48 Carboxylic Acids and Their Derivatives, 48 (a) Esters, 48 (b) Thioesters, Thioamides, and Thiocyanates, 51 (c) Amides, Amidines, and Peptides, 52 (d) -Lactams, 56 Phosphoric Acids and Their Derivatives, 58 (a) Phosphate Monoesters and Diesters, 58 (b) Triesters, 61 References, 62 Intermolecular Catalysis and Reactions Carboxylic Acids and Their Derivatives (a) Esters (i) Transesterification Two articles address green chemistry issues, one investigating recycling of polycarbonates and the other investigating plant-derived alternatives to fossil fuels. Polycarbonates are widely used thermoplastics, one of the more common ones being the polymer (1) (Scheme 1) formed from reaction between 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and phosgene. Its methanol- ysis would regenerate monomer bisphenol A (2) and produce, as by-product, dimethyl carbon- Organic Reaction Mechanisms 2019, First Edition. Edited by M. G. Moloney. © 2023 John Wiley & Sons Ltd. Published 2023 by John Wiley & Sons Ltd. 44 Organic Reaction Mechanisms 2019 O O O O O O (1) HO OH (2) MeO OMe (3) + MeOH O Scheme 1 ate (3), a widely used solvent and industrial chemical intermediate (Scheme 1).
eBook - PDF- Allan Blackman, Steven E. Bottle, Siegbert Schmid, Mauro Mocerino, Uta Wille(Authors)
- 2022(Publication Date)
- Wiley(Publisher)
In these examples, the reagents convert OH groups to chlorides. Solution (a) Cl O + SO 2 + HCl (b) Cl HCl O + + POCl 3 Is our answer reasonable? The two principal Reactions of Carboxylic Acids are breaking the OH bond (acid dissociation) and breaking the COH bond (nucleophilic acyl substitution). In this case, it is the latter, so the products should show this; that is, has the OH group been replaced with Cl? PRACTICE EXERCISE 23.6 Complete each of the following equations. (a) + SOCl 2 OH Br O (b) O OH HO O + 2PCl 5 Reactions with alcohols The reaction of carboxylic acids and their derivatives with alcohols is important for the preparation of esters. We will discuss the esterification reaction starting with the reaction of carboxylic acids with alcohols. We will then investigate the reactions of acid chlorides, acid anhydrides, esters and amides with alcohols. Carboxylic acids — the Fischer esterification Treatment of a carboxylic acid with an alcohol in the presence of an acid catalyst (most commonly, concentrated sulfuric acid) gives an ester. This method of forming an ester is given the special name Fischer esterification after the German chemist Emil Fischer (1852–1919; Nobel Prize in chemistry, 1902). As an example of a Fischer esterification, treating acetic acid with ethanol in the presence of concentrated sulfuric acid gives ethyl acetate, a common solvent (figure 23.5), and water. acetic acid ethanol ethyl acetate (ethyl ethanoate) H 2 SO 4 + H 2 O + OH O OH O O 1204 Chemistry FIGURE 23.5 Ethyl acetate is the solvent used in nail polish remover. Acid-catalysed esterification is reversible, and generally, at equi- librium, significant quantities of carboxylic acid and alcohol remain. By controlling the experimental con- ditions, however, we can use Fischer esterification to prepare esters in high yields.
eBook - PDFOrganic Reaction Mechanisms 2017
An annual survey covering the literature dated January to December 2017
- A. C. Knipe, Mark G. Moloney, A. C. Knipe, Mark G. Moloney(Authors)
- 2020(Publication Date)
- Wiley(Publisher)
63 2 Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and their Derivatives C. T. Bedford Department of Chemistry, University College London, London, UK CHAPTER MENU Intermolecular Catalysis and Reactions, 63 Carboxylic Acids and their Derivatives, 63 (a) Acids, 63 (b) Esters and lactones, 65 (i) Solvolysis reactions, 65 (c) Acyl halides and anhydrides, 67 (d) Carbonates and carbamates, 67 (e) Thiocarbonates, 69 Phosphoric Acids and their Derivatives, 70 (a) Phosphonates, 70 (b) Phosphoramidates, phosphonamidates, and phosphinamidates, 71 (c) Phosphinamidyl halides, 73 (d) Thiophosphinates and thiophosphonyl halides, 74 Sulfonic Acids and their Derivatives, 75 (a) Sulfonyl halides, 75 Association-Prefaced Catalysis, 75 Biologically Significant Reactions, 76 Carboxylic Acids and their Derivatives, 76 (a) Acids, 76 (b) Esters, 78 (c) Amides, peptides, and carbamates, 80 (i) 𝛽 -Lactams, 83 Phosphoric Acids and their Derivatives, 87 (a) Phosphates, 87 (b) Phosphoramidates, 90 References, 91 Intermolecular Catalysis and Reactions Carboxylic Acids and their Derivatives (a) Acids A one-pot synthesis of thioesters ( 4 ) from carboxylic acids can be achieved by the reaction of the acid ( 1 ) with a primary alkyl halide ( 2 ), N , N ′ -diphenylthiourea ( 3 ), and trimethylamine under microwave-assisted heating in the presence of a catalytic amount of 4-dimethylaminopyridine Organic Reaction Mechanisms 2017, First Edition. Edited by A. C. Knipe and M. G. Moloney. © 2020 John Wiley & Sons Ltd. Published 2020 by John Wiley & Sons Ltd. 64 Organic Reaction Mechanisms 2017 R 1 OH C O ( 1 ) + R 2 –X + PhNH NHPh S ( 3 ) ( 2 ) NEt 3 , cat. DMAP microwave, 433 K, 30 min R 1 S C O ( 4 ) R 2 R 1 = aryl, alkyl R 2 = benzyl, allyl, primary alkyl X = Cl, Br Scheme 1 BnNEt 3 ( 5 ) + − Cl cat.
eBook - PDFOrganic Reaction Mechanisms 2016
An annual survey covering the literature dated January to December 2016
- A. C. Knipe(Author)
- 2019(Publication Date)
- Wiley(Publisher)
CHAPTER 2 Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and their Derivatives C. T. Bedford Department of Chemistry, University College London, London, UK INTERMOLECULAR CATALYSIS AND REACTIONS . . . . . . . . . . . . . . 71 Carboxylic Acids and their Derivatives . . . . . . . . . . . . . . . . . . . . . . . . 71 (a) Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71 (b) Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73 (i) Transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . 73 (ii) Solvolysis reactions . . . . . . . . . . . . . . . . . . . . . . . . . . 73 (iii) Aminolysis reactions . . . . . . . . . . . . . . . . . . . . . . . . . 75 (c) Acyl Halides and Anhydrides . . . . . . . . . . . . . . . . . . . . . . . . . 76 (d) Amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 (e) Carbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 (f) Thioesters and Thiocarbonates . . . . . . . . . . . . . . . . . . . . . . . . . 80 (g) Thioamides and Thioacyl Halides . . . . . . . . . . . . . . . . . . . . . . . 80 Phosphoric Acids and their Derivatives . . . . . . . . . . . . . . . . . . . . . . . . 82 (a) Phosphinic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 (b) Phosphoryl and Thiophosphoryl Halides . . . . . . . . . . . . . . . . . . . 82 INTRAMOLECULAR CATALYSIS AND NEIGHBOURING GROUP PARTICIPATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 BIOLOGICALLY SIGNIFICANT REACTIONS . . . . . . . . . . . . . . . . . . . 87 Carboxylic Acids and their Derivatives . . . . . . . . . . . . . . . . . . . . . . . . 87 (a) Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 (b) Amides and Peptides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 Phosphoric Acids and their Derivatives .
eBook - PDFOrganic Reaction Mechanisms 2015
An annual survey covering the literature dated January to December 2015
- A. C. Knipe(Author)
- 2019(Publication Date)
- Wiley(Publisher)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 BIOLOGICALLY SIGNIFICANT REACTIONS . . . . . . . . . . . . . . . . . . . 89 Carboxylic Acids and their Derivatives . . . . . . . . . . . . . . . . . . . . . . . . 89 (a) Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 (b) Esters and Lactones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 (c) Amides, Ureas, and Peptides . . . . . . . . . . . . . . . . . . . . . . . . . 94 (d) Lactams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98 Phosphoric Acids and their Derivatives . . . . . . . . . . . . . . . . . . . . . . . . 99 (a) Phosphate Monoesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100 (b) Phosphate Diesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102 (c) Phosphate Triesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 (d) Phosphonyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 Sulfonic Acids and their Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . 104 (a) Sulfates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105 Organic Reaction Mechanisms 2015, First Edition. Edited by A. C. Knipe. © 2019 John Wiley & Sons Ltd. Published 2019 by John Wiley & Sons Ltd. 73 74 Organic Reaction Mechanisms 2015 INTERMOLECULAR CATALYSIS AND REACTIONS Carboxylic Acids and their Derivatives (a) Esters (i) Transesterification Reactions of a series of potassium aryl oxides XC 6 H 4 O − K + with 3-nitro- and 2,4- dinitro-benzoates in 50 mol% DMF/50 mol% H 2 O were interpreted as proceeding via a spiro--complex (1) (Scheme 1) in an S N Ar reaction.
eBook - PDFOrganic Reaction Mechanisms 2018
An Annual Survey Covering the Literature Dated January to December 2018
- Mark G. Moloney(Author)
- 2021(Publication Date)
- Wiley(Publisher)
51 2 Reactions of Carboxylic, Phosphoric and Sulfonic Acids and their Derivatives C. T. Bedford Department of Chemistry, University College London, London, WC1H 0AJ, UK CHAPTER MENU Intermolecular Catalysis and Reactions, 51 Carboxylic Acids and their Derivatives, 51 Esters, 51 Anhydrides, 52 Amides, 52 Carbonates and Carbamates, 53 Sulfonic Acids and their Derivatives, 55 Sulfonates and Sulfonyl Halides, 55 Intramolecular Catalysis, 56 Association-prefaced Catalysis, 59 Biologically Significant Reactions, 60 Carboxylic Acids and their Derivatives, 60 Amides and Peptides, 60 Phosphoric Acids and their Derivatives, 61 Phosphate and Boranephosphonate Diesters, 61 Phosphate Triesters, 63 References, 67 Intermolecular Catalysis and Reactions Carboxylic Acids and their Derivatives Esters Transesterification Reactions Efficient Bu t ONa-catalyzed transesterification was shown to occur between t -butyl acetate ( 1 ; R ′ = Me) or benzoate ( 1 ; R ′ = Ph) and primary or secondary alcohols ( 2 ) by heating a mixture of the two with the base at 373 K for 1 h in toluene (Scheme 1). When the t -butyl ester ( 1 ; R ′ = Me, Ph) was used in two-fold excess in the presence of 2 mol% Bu t ONa ( 3 ), the yields of both the acetate ( 4 ; R ′ = Me) and the benzoate ( 4 ; R ′ = Ph) were very good to excellent. Preliminary mechanistic studies using a secondary alcohol as a prototype showed that treating diphenyl-methanol ( 5 ) (1.1 equiv) with Bu t ONa ( 3 ) in toluene at 373 K for 1 h yielded its sodium salt as a crystalline (known) hexameric aggregate ( 6 ) in 44% yield (Scheme 2; A ), though none was formed by similar treatment of the alcohol ( 5 ) at room temperature for 12 h ( B ). The purified hexameric salt ( 6 ) was then reacted with t -butyl acetate ( 7 ) (2 equiv) for 1 h in toluene at 373 K Organic Reaction Mechanisms 2018, First Edition. Edited by M. G. Moloney. © 2021 John Wiley & Sons Ltd. Published 2021 by John Wiley & Sons Ltd.
eBook - PDF- David R. Klein(Author)
- 2016(Publication Date)
- Wiley(Publisher)
926 CHAPTER 20 Carboxylic Acids and Their Derivatives The accepted mechanism is exactly what we would expect for a nucleophilic acyl substitution that takes place under acidic conditions. Evidence for this mechanism comes from isotopic labeling experiments in which the oxygen atom of the alcohol is replaced with a heavier isotope of oxygen ( 18 O), and the location of this isotope is tracked throughout the reaction. The location of the isotope in the product (shown in red) supports Mechanism 20.6. R OH O MeO * H R O * Me O H 2 O [H + ] O = 18 O * + + The Fischer esterification process is reversible and can be controlled by exploiting Le Châtelier’s prin- ciple. That is, formation of the ester can be favored either by using an excess of the alcohol (i.e., using the alcohol as the solvent) or by removing water from the reaction mixture as it is formed. R OH O R OMe O H 2 O Can be removed from the mixture [H + ] Excess MeOH + The reverse process, which is conversion of the ester into a carboxylic acid, can be achieved by using an excess of water, as we will see in Section 20.11. Preparation of Esters via Acid Chlorides Esters can also be prepared by treating an acid chloride with an alcohol. We already explored this reaction in Section 20.8. R Cl O R OR O ROH Pyridine LOOKING BACK Le Châtelier’s principle states that a system at equilibrium will adjust in order to minimize any stress placed on the system. CONCEPTUAL CHECKPOINT 20.20 In this section, we have seen three ways to achieve the fol- lowing transformation. Identify the reagents necessary for all three methods. OH O OEt O ? ? ? 20.21 Identify reagents that can be used to accomplish each of the following transformations: (a) OH O OEt (b) O OEt 20.11 Reactions of Esters Saponification Esters can be converted into carboxylic acids by treatment with sodium hydroxide followed by an acid. This process is called saponification (Mechanism 20.7): R OR O R OH O ROH 1) NaOH 2) H 3 O + +
eBook - PDFOrganic Reaction Mechanisms 1966
An annual survey covering the literature dated December 1965 through November 1966
- B. Capon, M. J. Perkins, C. W. Rees, B. Capon, M. J. Perkins, C. W. Rees(Authors)
- 2008(Publication Date)
- Wiley-Interscience(Publisher)
CHAPTER 12 Reactions of Acids and their Derivatives’ Carboxylic Acids The relative importance of nucleophilic and general base-catalysis by acetate ion in the hydrolysisof a series of aryl acetateshas been determined by trapping with aniline the acetic anhydride which is an intermediate in the nucleo- philically catalysed reaction.2 Nucleophilic catalysis predominates with acetates of phenols having a pK, < 5 but could not be detected with those of phenols with pK, > 8. This is reasonable if the nucleophilic catalysis involves a tetrahedral intermediate which can partition by returning to reactants or by going on to yield acetic anhydride [equation (l)]. 0- kp (1) ki I I ArOCO-Me + -0Ac ArO-4-Me ArO- + AczO k-i OAc With phenols of low acidity the stability of the leaving phenoxide ion is also low and it will be a poor leaving group; hence the intermediate partitions exclusively to yield reactants i.e., k-l s- k2. The rate of the general base- catalysed reaction also increases with decreasing pK, of the phenol but not so much as the rate of the nucleophilically catalysed reaction. The difference in solvent isotope effect for the two mechanisms is quite small. Thus with 2,4-dinitrophenylacetate which reacts exclusively with nucleophilic catalysis k0Ac(H20)/ko,c(D20) = 1.8, and with p-tolyl acetate which reacts with exclusive general base-catalysis it is 2.4. The entropies of activation for the general base-catalysed reactions (ca. -32 e.u.) appear, however, to be sig- nificantly more negative than those for the nucleophilicallycatalysed reactions (ca. -10 e.u.) and the difference is approximately that to be expected for the inclusion of one extra water molecule in the transition state for the former.
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