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Nomenclature of Carboxylic Acids • Select the Longest Carbon Chain Containing the Carboxyl Group

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Nomenclature of Carboxylic Acids • Select the Longest Carbon Chain Containing the Carboxyl Group Chapter 5 Carboxylic Acids and Esters Carboxylic Acids • Carboxylic acids are weak organic acids which Chapter 5 contain the carboxyl group (RCO2H): Carboxylic Acids and Esters O C O H O RCOOH RCO2H Chapter Objectives: O condensed ways of • Learn to recognize the carboxylic acid, ester, and related functional groups. RCOH writing the carboxyl • Learn the IUPAC system for naming carboxylic acids and esters. group a carboxylic acid C H • Learn the important physical properties of the carboxylic acids and esters. • Learn the major chemical reaction of carboxylic acids and esters, and learn how to O predict the products of ester synthesis and hydrolysis reactions. the carboxyl group • Learn some of the important properties of condensation polymers, especially the polyesters. Mr. Kevin A. Boudreaux • The tart flavor of sour-tasting foods is often caused Angelo State University CHEM 2353 Fundamentals of Organic Chemistry by the presence of carboxylic acids. Organic and Biochemistry for Today (Seager & Slabaugh) www.angelo.edu/faculty/kboudrea 2 Nomenclature of Carboxylic Acids • Select the longest carbon chain containing the carboxyl group. The -e ending of the parent alkane name is replaced by the suffix -oic acid. • The carboxyl carbon is always numbered “1” but the number is not included in the name. • Name the substituents attached to the chain in the Nomenclature of usual way. • Aromatic carboxylic acids (i.e., with a CO2H Carboxylic Acids directly connected to a benzene ring) are named after the parent compound, benzoic acid. O C OH 3 4 Benzoic acid Examples: Naming Carboxylic Acids Examples: Naming Carboxylic Acids • Name the following compounds: • Name the following compounds: O O O Br O HCOH CH3 COH COH CH3CHCH2 COH CH3CH2CHCH3 O O HO CCH2CH2CH3 CH3CH2 COH CH3 O CH3CHCH2 COH CH2CH2CH3 5 6 Chapter 5 Carboxylic Acids and Esters Examples: Naming Carboxylic Acids Examples: Naming Carboxylic Acids • Name the following compounds: • Name the following compounds: CH 3 CO H O 2 O CH O COH 3 COH CH C OH CH3CCH3 CH3 O Cl CH2CH2CHCH3 CH3 C OH 7 CH3CHCH3 8 More Complicated Acids Examples: Drawing Carboxylic Acids • For molecules with two carboxylic acid groups the • Draw structural formulas for the following molecules: carbon chain in between the two carboxyl groups – 2-methylpropanoic acid (including the carboxyl carbons) is used as the longest chain; the suffix -dioic acid is used. • For molecules with more than two carboxylic acid groups, the carboxyl groups are named as carboxylic – 2,2,5-trimethylhexanoic acid acid substituents. O O O O HOC C OH – 4,5-dimethyl-3-nitrooctanoic acid ethanedioic acid HO C CH2 CH CH2 C OH O O C OOH HO C CH2 C OH propane-1,2,3-tricarboxylic acid propanedioic acid 9 10 Examples: Drawing Carboxylic Acids • Draw structural formulas for the following molecules: – para-bromobenzoic acid – 2,4,6-trinitrobenzoic acid – 4-ethylpentanedioic acid (what’s wrong with this name?) 11 12 Chapter 5 Carboxylic Acids and Esters Physical Properties of Carboxylic Acids • Carboxylic acids hydrogen bond to themselves to form a dimer: O H O RC C R Physical Properties of O H O • Carboxylic acids also form hydrogen bonds to Carboxylic Acids water molecules: H H O O RC H O H O 13 14 H Physical Properties of Carboxylic Acids Physical Properties of Carboxylic Acids • Since carboxylic acids can form more than one set of • As the number of carbons in a carboxylic acid series hydrogen bonds, their boiling points are usually becomes greater, the boiling point increases and the higher than those of other molecules of the same solubility in water decreases. molecular weight (MW). • Many carboxylic acids that are liquids at room • Low-MW carboxylic acids are generally liquids at temperature have characteristically sharp or room temp. (often, they are somewhat oily); higher- unpleasant odors. MW carboxylic acids are generally waxy solids. – Ethanoic acid/acetic acid is the main ingredient in • Carboxylic acids with 12 to 20 carbon atoms are vinegar. often referred to as fatty acids, since they are found in the triglycerides in fats and oils (more later). – Butanoic acid is partially responsible for the odor of locker rooms and unwashed socks. • Short-chain carboxylic acids are also generally more soluble in water than compounds of similar MW, – Hexanoic acid is responsible for the odor of since they can hydrogen bond to more than one Limburger cheese. water molecule. • Like most acids, carboxylic acids tend to have a sour 15 taste (e.g., vinegar, citric acid, etc.) 16 Table 5.2 Physical properties of some carboxylic acids Boiling Points of Various Functional Groups Common Structural BP MP Solubility Name Formula (°C) (°C) (g/100 mL H2O) Formic acid H—CO2H 101 8 Infinite Acetic acid CH3—CO2H 118 17 Infinite Propionic acid CH3CH2—CO2H 141 -21 Infinite Butyric acid CH3(CH2)2—CO2H 164 -5 Infinite Valeric acid CH3(CH2)3—CO2H 186 -34 5 Caproic acid CH3(CH2)4—CO2H 205 -3 1 Caprylic acid CH3(CH2)6—CO2H 239 17 Insoluble Capric acid CH (CH ) —CO H 270 32 Insoluble Figure 5.4 3 2 8 2 The boiling points of Lauric acid CH3(CH2)10—CO2H 299 44 Insoluble carboxylic acids compared Myristic acid CH3(CH2)12—CO2H Dec. 58 Insoluble to 1° alcohols, aldehydes Palmitic acid CH (CH ) —CO H Dec. 63 Insoluble and ketones, ethers and 3 2 14 2 alkanes. Stearic acid CH3(CH2)16—CO2H Dec. 71 Insoluble 17 18 Chapter 5 Carboxylic Acids and Esters Comparing Physical Properties Examples: Predicting Physical Properties Boiling Point: Water Solubility: • Arrange the following compounds in order of Carboxylic acid increasing boiling point. (All of the compounds Carboxylic acid have about the same molecular weight.) Alcohols Alcohols Aldehydes/Ketones Aldehydes/Ketones – 1-pentanol Ethers Ethers – hexane Alkanes Alkanes – butanoic acid – pentanal Name Molecular Boiling Solubility in water weight point • Which member of each of the following pairs of Pentane 72 g/mol 35°C Insoluble compounds would you expect to have a higher Diethyl ether 74 g/mol 35°C Insoluble solubility in water? Butanal 72 g/mol 76°C 7.1 g / 100 mL H2O – 2-butanone or propanoic acid 1-Butanol 74 g/mol 118°C 9.1 g / 100 mL H2O – hexanoic acid or ethanoic acid Propanoic acid 74 g/mol 141°C Infinite 19 20 Important Carboxylic Acids O O O CH3CH2 C OH HOHC CH3 C OH Propanoic acid Methanoic acid Ethanoic acid (Propionic acid) (Formic acid) (Acetic acid) Found in Swiss cheese; (from Latin formica, ant) (from Latin acetum, vinegar) salts of this acid are used A component of the venom Vinegar is a 5% solution of as mold inhibitors of ants and caterpillars; acetic acid dissolved in water; produced in the body when acetic acid is also responsible methanol is consumed for the taste of sour wine (from Some Important the oxidation of ethanol) and sourdough bread Carboxylic Acids O O CH3CH2CH2 C OH CH3CH2CH2CH2CH2 C OH Butanoic acid Hexanoic acid (Butyric acid) (Caproic acid) (from Latin butyrum, butter) Responsible for the odor of This acid has a foul, rancid odor; Limburger cheese. produced from the breakdown of soft triglycerides in butter 21 22 O O OH O O OH HO HO OH OH O O OH H N Glycolic acid 2 An alpha-hydroxy acid used in OH 2-hydroxy-1,2,3-propanetricarboxylic acid cosmetics and skin creams; para-Aminobenzoic aid (PABA) OH (Citric acid) Used in sunscreens; absorbs alpha-hydroxy acids are thought to Found in citrus fruits (lemons, grapefruit, short-wavelength UV light. It is also required loosen the cells of the epidermis and 2-hydroxypropanoic acid oranges, etc.); commonly used in buffering by bacteria for the production of folic acid, accelerate the flaking off of dead skin; (Lactic acid) solutions with sodium citrate needed to maintain the growth of healthy cell however these compounds can increase Produced from the fermentation of sugars walls; sulfa drugs block the uptake of PABA the skin's sensitivity to UV light under anaerobic conditions; found in sweat, by bacteria, causing them to be unable to sour milk, fermented pickles, sauerkraut, manufacture folic acid, and thus preventing and yogurt; produced in muscles from O O glucose under anaerobic conditions (the the bacteria from multiplying O buildup of lactic acid leads to a heavy, weak feeling, and muscle cramps); produced after O O HO HO OH OH death during the breakdown of sugars in the Oxalic acid body by bacteria, inactivating the enzymes Found in many leafy green plants O OH that allow the transport of calcium ions, HO OH such as rhubarb and spinach; Malic acid causing rigor mortis combines with calcium ions in the Terephthalic acid Responsible for the sharp body to produce insoluble salts, A white, crystalline solid; used in taste of apples (genus Malus) which form kidney stones the manufacture of some polyesters 23 24 Chapter 5 Carboxylic Acids and Esters O OH O O HO H2N OH OH OH O OH Gamma-aminobutanoic acid (GABA) N A inhibitory neurotransmitter; ethanol binds to the same Niacin Tartaric acid protein as GABA at a neighboring location, distorting the A water-soluble, B-Complex vitamin obtained Found naturally in wine, and is protein so that GABA binds more easily, further inhibiting the from fish, green vegetables, lean meat, poultry, responsible for some of the sharp taste of cell from firing; benzodiazepines such as Valium also bind to whole-grain and enriched bread and cereal; wine; it is added to many sour-tasting the same protein but at a different site, inhibiting the cell still produced in the body from tryptophan; sweet foods.
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