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6| Carboxylic acids, Esters, Fats and Oils
Unit 6 Carboxylic acids, Esters, Fats and Oils 6.1 Introduction Carboxylic acids (RCOOH), esters (RCOOR'), Lipids (fats and oils), all three families of organic compounds occur widely in nature, and many useful synthetic compounds have been prepared as well. Simple carboxylic acids like acetic acid (CH3COOH) have a sour taste and a biting odor, and long-chain carboxylic acids form vegetable oils and animal fat. Simple esters have easily recognized fragrances, and the most abundant lipids contain three ester groups and we look into each of them in this chapter. 6.2 Carboxylic acids Structure of carboxylic acids Carboxylic acids are weak organic acids which contain the carboxyl group (RCO2H) as a functional group. The tart flavor of sour-tasting foods is often caused by the presence of carboxylic acids.
Chemistry for Grades 11 & 12
A carboxylic acid the carboxyl group condensed ways of writing the carboxyl group Carboxylic acids are classified according to the substituent that is bonded to the carboxyl carbon: Aliphatic acids have an alkyl group bound to the carboxyl group. An aromatic acid has an aryl group bound to the carboxyl group.
Aliphatic carboxylic acids
Aromatic carboxylic acids A carboxylic acid donates protons by the heterolytic cleavage of the O-H bond, generating a carboxylate ion like in the following reaction
To consider the shape of carboxyl group lets consider the simplest carboxylic acid which is formic acid. The most stable conformation of formic acid is an almost planar arrangement of the molecule.
Bond angles of formic acid Bond lengthes of formic acid The carbon is sp2hybridized, and the O-H bond lies in the plane described by the sp2 carbon, eclipsing the C=O double bond. This unexpected geometric arrangement can be explained by resonance (or conjugation). Three resonance forms can be written for formic acid.
Major structure Minor structure Very minor structure The second structure requires the C-O-H bonds to be co-planar. One of the unshared lone pairs of oxygen is delocalized into the electrophilic system of the carbonyl group. (One of the lone pairs on the hydroxyl oxygen is conjugated with the C=O double bond). 6.2.1 Nomenclature of Carboxylic Acids Carboxylic acids have IUPAC names and common names as organic molecules. So let us start with the IUPAC names and we will summarize with the common names.
IUPAC formulation The root name is based on the longest continuous chain of carbon atoms bearing the carboxyl group. The -e is replaced by -oic acid. The chain is numbered starting with the carboxyl carbon atom.
The carboxyl group takes priority over any other functional groups. Example Name the following branched chain carboxylic acid
Solution Find and name the longest chain containing COOH.
Number and name the substituents, making sure the COOH group is at C1.
two methyl substituents on C4 and C5 so the Answer will be 4,5dimethylhexanoic acid Other examples of branched carboxylic acids are
3-methylpentanoic acid
2-hydroxybutanoic acid
2-prophylpentanoic acid
2-cyclohexylpropanoic acid
4-aminobutanoic acid Cycloalkanes with carboxyl substituents are named as cycloalkanecarboxylic acids.
3,3-dimethylcyclohexanecarboxylic acid (Notice that CO H as a substituent makes the carbon it is bound

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to C-1, not itself). N.B all the above kinds of carboxylic acids can be named generally as saturated monocarboxylic acids as they contain only one carboxyl group and saturated bonds (single bonds). Example Name the following aromatic (benzene ring containing) carboxylic acids
Solution Aromatic acids of the form Ar-CO2H are named as derivatives of benzoic acids, with ortho, meta and para indicating the location relative to the carboxyl group. Ortho is the first position next to the carboxyl group, Meta is after ortho and Para is after meta.
Benzoic acid
Para-aminobenzoic acid
Ortho-hydroxybenzoic acid Example Name the following dicarboxylic acid
Solution Aliphatic dicarboxylic acids are named by simply adding the suffix -dioic acid to the root name. The root name comes from the longest carbon chain containing both carboxyl groups. Numbering starts at the end closest to a substituent.
3-bromohexanedioic acid butanedioic acid
benzenedioic acid (phthalic acid) N.B For molecules with more than two carboxylic acid groups, the carboxyl groups are named as carboxylic acid substituents.
propane-1,2,3-tricarboxylic acid The tables below will summarize the common and IUPAC names of monocarboxylic and dicarboxylic acids.
Table 6.1 Common and IUPAC names of dioic (dicarboxylic) acids.
Table 6.2 Common and IUPAC names of Monocarboxylic acids. 6.2.2 Physical properties of carboxylic acids Carboxylic acids hydrogen bond to themselves to form a dimer:
Carboxylic acids also form hydrogen bonds to water molecules: H
Since carboxylic acids can form more than one set of hydrogen bonds, their boiling points are usually higher than those of other molecules of the same molecular weight (MW). Low-MW carboxylic acids are generally liquids at room temp. (often, they are somewhat oily); higher- MW carboxylic acids are generally waxy solids. Carboxylic acids with 12 to 20 carbon atoms are often referred to as fatty acids, since they are found in the triglycerides in fats and oils (more later). Short-chain carboxylic acids are also generally more soluble in water than compounds of similar MW, since they can hydrogen bond to more than one water molecule. As the number of carbons in a carboxylic acid series becomes greater, the boiling point increases and the solubility in water decreases. Carbons 1-4 = water soluble Carbons 5-8 = slightly water soluble Carbons 8 and above = virtually insoluble in water
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Many carboxylic acids that are liquids at room temperature have characteristically sharp or unpleasant odors. Ethanoic acid/acetic acid is the main ingredient in vinegar. Butanoic acid is partially responsible for the odor of locker rooms and unwashed socks. Hexanoic acid is responsible for the odor of Limburger cheese. Like most acids, carboxylic acids tend to have a sour taste (e.g., vinegar, citric acid, etc.) Carboxylic acids are generally weak acids; that is, they are only slightly ionized in water. Carboxylic acids have higher water solubility and boiling point while comparing them to the following organic molecules. Boiling point water solubility Carboxylic acid Carboxylic acid Alcohols Aldehydes / Ketones Ethers Alkanes Alcohols Aldehydes / Ketones Ethers Alkanes
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Table 6.3 Summary of main physical properties of carboxylic acids. 6.2.3 Chemical properties of carboxylic acids Acid-Base Reactions Because of their ability to form hydrogen ions in solution, carboxylic acids in general have the following properties: 1. Sour taste 2. Change blue litmus to red and affect other suitable indicators. 3. Form water solutions with pH values less than 7.
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Carboxylic acid carboxylate ion - At the physiological pH of 7.4 (the pH of most body fluids) the carboxylate form of most carboxylic acids is the predominate form. 4. Undergo neutralization reactions with bases to form water and a salt. Carboxylic acids react with strong bases such as sodium hydroxide (NaOH) and potassium hydroxide (KOH) to produce carboxylate salts. Carboxylate salts are named by naming the metal first and changing the -ic acid ending of the carboxylic acid name to -ate.
carboxylic acid
base
metal carboxylate
Sodium ethanoate (sodium acetate) Substitution reaction An ester is formed by the reaction of an acid with an alcohol or a phenol; water is also produced in the reaction. The overall transformation is that the -OH of an acid is replaced by the -OR' of an alcohol, the reaction is also known as The Fischer Esterification
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acid + alcohol ester + water
Reduction of Carboxylic Acids Lithium aluminum hydride reduces carboxylic acids back to primary alcohols.
The reaction proceeds through an aldehyde but it cannot be stopped at that stage since aldehydes are more easily reduced than carboxylic acid. Carboxylic acids are also reduced by borane (BH ) to generate
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primary alcohols. 6.2.4 Preparation of carboxylic acids Carboxylic acids can be synthesized in different ways however, lets see three reactions for the preparation of carboxylic acids all involving oxidation. (A) Oxidation of primary alcohols and aldehydes These oxidations are best performed using chromic acid (made from Na Cr O and H SO ). Potassium
2 2 7 2 4
permanganate can be used but gives lower yields.
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Primary alcohol
[O] = Cr2O7-2
(B) Oxidative cleavage of alkenes and alkynes Alkenes react with concentrated KmnO4 to produce intermediate glycols which react further to produce either carboxylic acids or ketones (depending on the original alkene substituents).
Not isolated
(C) Side chain oxidation of alkyl benzenes Benzoic acid derivatives can be made by the oxidation of alkylbenzenes with either hot KMnO4 or hot chromic acid with vigorous conditions, which means this can only be used when there are no oxidizable groups present in the molecule.
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toluene
sodium benzoate
ethyl benzene
sodium benzoate
Some important Carboxylic Acids Ethanoic acid (Acetic acid)(CH3COOH) (from Latin acetum, vinegar): Vinegar is a 5% solution of acetic acid dissolved in water; acetic acid is also responsible for the taste of sour wine (from the oxidation of ethanol) and sourdough bread. Butanoic acid (Butyric acid)(CH3CH2CH2COOH) (from Latin butyrum, butter) This acid has a foul, rancid odor; produced from the breakdown of soft triglycerides in butter. para-Aminobenzoic aid (PABA) Used in sunscreens; absorbs short-wavelength UV light. It is also required by bacteria for the
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production of folic acid, needed to maintain the growth of healthy cell walls; sulfa drugs block the uptake of PABA by bacteria, causing them to be unable to manufacture folic acid, and thus preventing the bacteria from multiplying.
Oxalic acid Found in many leafy green plants such as rhubarb and spinach; combines with calcium ions in the body to produce insoluble salts, which form kidney stones.
2-hydroxypropanoic acid (Lactic acid) Produced from the fermentation of sugars under anaerobic conditions; found in sweat, sour milk, fermented pickles, sauerkraut, and yogurt; produced in muscles from glucose under anaerobic conditions (the buildup of lactic acid leads to a heavy, weak feeling, and muscle cramps); produced after death during the breakdown of sugars in the body by bacteria, inactivating the enzymes that allow the transport of calcium ions, causing rigor mortis (Muscular stiffening that begins 2 to 4 hours after death and lasts for about 4 days).
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Pantothenic acid A water-soluble B-complex vitamin; converted by the body into Coenzyme A, which helps the body produce energy from food.
Some important Carboxylate Salts Sodium benzoate Found in cranberries and prunes; commonly used as a preservative in baked goods, ketchup, carbonated beverages, etc.
Sodium citrate The sodium salt of citric acid, sodium citrate, is used in buffers with citric acid to maintain desirable characteristics of foams and gels (jelly, ice cream, candy, whipped cream, etc.) by controlling the pH of the product; also used in medicines and blood for transfusions; also functions as an anticoagulant in blood.
Denatonium benzoate ('Bitrex') Benzyl diethyl ((2,6xylylcarbamoyl)methyl) ammonium benzoate Discovered in 1958, this is the bitterest-tasting compound known; as little as ten parts
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per million make substances unbearably bitter to most humans. It is used as an aversive agent, an additive that prevents accidental ingestion of a toxic substance. It is used to denature ethanol, methanol, and rubbing alcohol, and well as solvents, paints, arnishes, antifreeze, etc.
Fatty acids Fatty acids are carboxylic acids (RCOOH) with long carbon chains of 1220 carbon atoms. Because they have many nonpolar C-C and C-H bonds and few polar bonds, fatty acids are lipids, making them soluble in organic solvents and insoluble in water. Palmitic acid (C16H32) is a common 16-carbon fatty acid whose structure is given below.
Nonpolar C-C and C-H bonds The nonpolar part of the molecule (comprised of C-C and C-H bonds) is not attracted to water, so it is said to be hydrophobic (water fearing). The polar part of the molecule is attracted to water, so it is said to be hydrophilic (water loving). In a lipid, the
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hydrophobic portion is always much larger than the hydrophilic portion. Naturally occurring fatty acids have an even number of carbon atoms. There are two types of fatty acids. Saturated fatty acids have no double bonds in their long hydrocarbon chains. Unsaturated fatty acids have one or more double bonds in their long hydrocarbon chains. Generally, double bonds in naturally occurring fatty acids are cis (a cis alkene has two alkyl groups on the same side of the double bond, while a trans alkene has two alkyl groups on opposite sides of the double bond). The presence of cis double bonds affects the melting point of these fatty acids greatly and as the number of double bonds in the fatty acid increases, the melting point decreases. The cis double bonds introduce kinks in the long hydrocarbon chain, which makes it difficult for the molecules to pack closely together in a solid. The larger the numbers of cis double bonds, the more kinks in the hydrocarbon chain, and the lower the melting point.
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Table 6.4 Common fatty acids Some important Saturated Fatty Acids Lauric acid Found in coconut oil; commonly used in soaps
Stearic acid A saturated fatty acid found in lard, beef fat, butterfat, cottonseed oil; the sodium salt, produced by heating lard with sodium hydroxide, can be used as a soap.
Palmitic acid A fatty acid, found in lard, beef fat, butterfat, and cottonseed oil; the triglycerides in cocoa butter have oleic acid attached to the central oxygen, with stearic acid or palmitic acid on the other oxygens; this more regular composition gives cocoa butter a much sharper melting point than is usually observed in fats, and chocolate remains brittle almost up to its melting point of 34C (just below body temperature); the sudden melting of chocolate in the mouth gives it a pleasant feeling of coolness.
Some Unsaturated Fatty Acids Oleic acid An unsaturated fatty acid; the chain is much less flexible than that of stearic acid because of the double bond, and cannot pack as tightly, so the triglycerides it forms are oils and not fats; found in olive oil, cocoa butter and chocolate, beef fat, lard, and peanut oil.
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Eicosapentaenoic acid A omega-3 (Unsaturated fatty acids are sometimes classified as omega-n acids, where n is the carbon at which the first double bond occurs in the carbon chain, beginning at the end of the chain that contains the CH3 group. Thus, linoleic acid is an omega-6 acid and linolenic acid is an omega-3 acid.) polyunsaturated fatty acid found in fish oil and seafoods; omega-3 fatty acids may, according to some studies, help to lower the risk of heart disease.
Docosahexaenoic acid An omega-3 polyunsaturated fatty acid found in fish oil and seafoods
6.3 Esters Structure, source and formation of esters Esters are carbonyl compounds that contain an alkoxy group (OR') bonded to the carbonyl carbon. The structure of an ester is often abbreviated as RCOOR' or RCO2R'.
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Ester
methyl acetate
CH3CO2CH3 When carboxylic acids are combined with alcohols in the presence of an acid catalyst they react to form esters and water. The name of an ester indicates the acid and the alcohol that combined to form it. The first word in the name comes from the alkyl group of the alcohol, and the second word is the name of the acid. Many esters are colorless liquids with pleasant, fruity aromas. The aroma and flavor of many foods are due to the presence of esters. Example Carboxylic acid
Alcohol
Ester
Water
propanoic acid
ethanol
ethyl propanoate
water
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Carboxylic acids and esters are called acyl compounds, since they contain an acyl group (RCO) bonded to an electronegative atom like oxygen. The two most important features of acyl compounds, like other carbonyl compounds, are the following:
trigonal planar polar bond The carbonyl carbon is trigonal planar, so all bond angles are 120. The electronegative oxygen atom makes the carbonyl group polar, so the carbonyl carbon is electron poor (+) and the carbonyl oxygen is electron rich (). Oxalic acid (a carboxylic acid) in spinach and propyl acetate (an ester) in pears are examples of acyl compounds. 6.3.1 Nomenclature of esters The names of esters are derived from the names of the parent carboxylic acids. Keep in mind that the common names formic acid, acetic acid, and benzoic acid are used for the parent acid, so these common parent names are used for their derivatives as well. An ester has two parts to its structure, each of which must be named separately: an acyl group that contains the carbonyl group (RCO ) and an alkyl group (designated as R') bonded to the oxygen atom, so during naming: Name the alkyl or aromatic portion contributed by the alcohol part first.
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The acid part is named as a carboxylic acid, with the -ic acid suffix changed to -ate. In the IUPAC system, esters are identified by the suffix -ate.
acid part
alcohol part
Example Give a systematic name for the ester CH3CO2CH2CH3. Step [1] Name the R' group bonded to the oxygen atom as an alkyl group. The name of the alkyl group, ending in the suffix -yl, becomes the first part of the ester name. In this case, a two carbon ethyl group is bonded to the ester oxygen atom.
ethyl group Step [2] Name the acyl group (RCO) by changing the -ic acid ending of the parent carboxylic acid to the suffix -ate. The name of the acyl group becomes the second part of the name. In this case, the name of the parent two-carbon carboxylic acid, acetic acid, becomes acetate. N.B - Esters are often written as RCOOR', where the alkyl group (R') is written last. When an ester is named, however, the R' group appears first in the name.
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derived from acetic acid (acetate) So the name of the ester will be ethyl acetate. Some other nomenclatures of esters are given below:
tert-butyl propanoate
vinyl acetate (ethenyl ethanoate)
methyl p-clorobenzoate
diethyl malonate
6.3.2 Physical properties of esters Simple esters derived from monocarboxylic acids and monohydroxy alcohols are colorless, generally nonpolar liquids or solids. Low- and intermediate-molar-mass esters (both acids and alcohols up to about 10 carbons) are liquid with characteristic (usually fragrant or fruity) odors. High-molar-mass esters (formed from acids or alcohols of 16 or more carbons) are waxes and are obtained from various plants. They are used in furniture wax and automobile wax preparations.
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Carnauba wax contains esters of 24-and 28- carbon fatty acids and 32- and 34-carbon alcohols. Esters cannot hydrogen bond to each other and therefore have lower boiling points than carboxylic acids. Esters can hydrogen bond to water and have appreciable water solubility.
Table 6.5 Summary of physical properties of esters 6.3.3 Chemical properties of esters Hydrolysis The most important reaction of esters is hydrolysis the splitting of molecules through the addition of water. A catalyst is often required for the acid or base hydrolysis reactions.
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Acid Hydrolysis The hydrolysis of an ester involves the reaction with water to form a carboxylic acid and an alcohol.
ester
alcohol
carboxylic acid
Alkaline Hydrolysis (Saponification) Saponification is the hydrolysis of an ester by a strong base (NaOH or KOH) to produce an alcohol and a salt (or soap if the salt formed is from a high-molar-mass acid). Notice that in saponification, the base is a reactant and not a catalyst.
Ester
alcohol 6.3.4 Preparation of Esters
salt
Synthesis of Esters: Esterification Reactions The simplest way to synthesize an ester is to heat a carboxylic acid with an alcohol or phenol (plus an acid catalyst); the oxygen of the alcohol adds to the carboxyl group, splitting out a molecule of water in the process (an esterification reaction). Acid catalyzed reaction of alcohols and carboxylic acids to form esters is also called Fischer esterification reaction.
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Fischer esterification is an equilibrium process. In this reaction ester formation is favored by use of a large excess of either the alcohol or carboxylic acid and is also favored by removal of water.
Example
acetic acid
ethanol
ethyl acetate
benzoic acid
methanol
methyl benzoate
Since this reaction is a reversible reaction, it often reaches an equilibrium with a large amount of unreacted starting material still present. Better yields are obtained using either acid chlorides or acid anhydrides as starting materials. These reactions are nonreversible.
Acid chloride
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Acid chloride alcohol or phenol Example
an ester
benzoyl chloride
ethyl benzoate (80%)
Acid anhydride
acid anhydride alcohol or phenol
an ester
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a carboxylic acid Example
acetic anhydride benzyl alcohol benzyl acetate acetic acid
phthalic anhydride sec-butyl alcohol phthalate (97%)
sec-butyl hydrogen
Condensation Polymers: Polyesters Condensation polymers are polymers which form with the loss of a small molecule (typically water or HCl). Condensation polymers, such as polyesters and polyamides (like Nylon), form when each of the monomers contain two of the same functional group, so the reaction can take place at both ends. Condensation polymers are formed by substitution reactions between neighboring monomers. The polyesters are joined by ester linkages between carboxylic acid and alcohol groups.
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The macromolecule formed may be linear or cross-linked Example
Polyethylene terephthalate (PET) A polyester Over 3 billion pounds of PET are made every year. It forms a very linear chain, and is very inert. It can be melted and pulled through spinnerettes to make fibers, threads, or yarn (Dacron, Fortrel, Terylene), where it can be used in automobile tire cord, permanent press clothing, sutures, replacements for damaged sections of blood vessels and the esophagus, etc. PET melts can also be forced through narrow slits to produce thin sheets or ribbons known as Mylar; this form is used as the support medium in audio and video tape. Some important Saturated Fatty Acids Salicylic acid Found in the bark of the willow tree (Salix); a tea brewed from the bark reduces fever and relives pain and inflammation, but is very acidic, and causes irritation of the mucous membranes in the mouth, throat, and stomach, and can cause painful ulcers and stomach bleeding.
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Aspirin (acetylsalicylic acid) Produced by reacting salicylic acid with acetic anhydride, giving a compound which is less acidic, and does not cause as much irritation, but still retains all of the beneficial medical properties; aspirin seems to work by blocking the production of prostaglandins, hormones which may be responsible for producing pain, fever and inflammation; one of the most commonly used pharmaceutical drugs; over 40 million pounds are produced in the United States per year.
Acetominophen Does not cause stomach irritation, and has analgesic and antipyretic properties that are similar to aspirin, but no anti-inflammatory functions; available under the trade names Tylenol, Excedrin Aspirin Free, Panadol, and Anacin-3.
Ibuprofen An analgesic, antipyretic, and anti-inflammatory drug; it is also not irritating to the stomach lining; available under the trade names Motrin, Advil, Ibuprin, Nuprin, and Mediprin.
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Some Important Phosphate Esters
Example DNA, deoxyribonucleic acid, stores the genetic information of an organism and transmits that information from one generation to another.
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6.4 Fats and oils It seems that every week brings new reports of the effects of dietary fats and oils on health. Many of these reports indicate that a diet high in fat is unhealthy, leading to heart disease and circulatory problems. As a result, grocery shelves are filled with food packages that proclaim their contents to be low fat or fat free. However, other reports caution that dietary fats are necessary for health, and that the chemical nature of the fats is
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important. We are admonished to be concerned about saturated versus unsaturated fats, to avoid the former and consume the latter. 6.4.1 Source and structure of fats and oils Fats and oils are naturally occurring esters. Fats and oils can be classified according to their origin as animal, vegetable or marine. At room temperature fats are solids whereas oils are liquids. The low melting points of oils are caused by more of their molecules being unsaturated i.e. containing carbon to carbon double bonds. Their degree of unsaturation is higher than that of fats as can be seen from the fact that oils decolourise bromine solution quickly. If the chains are saturated the molecules can pack neatly together, event at high temperatures. If the chains contain one, or more, double bonds, the zig-zag chains become more distorted and the molecules cannot pack closely together. Since the molecules are not packed as closely together they can be more easily separated as the van der Waals forces between the molecules will be smaller. This results in oils having lower melting and boiling points than fats. Animal sources generally provide fats, for example, dripping from beef, lard from pork and tallow from lamb. These fats are solid at room temperature and only become liquid when heated. Vegetable sources generally provide oils. Ester oils can be obtained from olives and seeds such as corn seed, sunflower seed, peanuts and soya beans which are liquids at room temperature. Marine sources can provide both fats and oils, Sea mammals providing fats and oils being obtained from fish.
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Fats and oils provide us with lots of energy. Fats and oils provide twice as much energy as sugars. As they contain so much energy eating too much can lead to obesity (More than average fatness). There is also mounting evidence that eating too much saturated fat can be linked to heart disease. Vitamins are contained in fatty foods such as butter whilst vegetable oils contain little in way of vitamins. The terminology applied to fats is based on the chemical structure of their molecules. Fats and oils belong to a group of biological substances called lipids. Lipids are biological chemicals that do not dissolve in water. They serve a variety of functions in organisms, such as regulatory messengers (hormones), structural components of membranes, and as energy storehouses. Fats and oils generally function in the latter capacity. Fats differ from oils only in that they are solid at room temperature, while oils are liquid. Fats and oils share a common molecular structure, which is represented by the formula below.
Long-chain carboxylic acids, often referred to as fatty acids, are stored by living organisms by combining them with glycerol to produce tri-esters called triglycerides. Triglycerides at room temperature are usually either solids or semi-solids (fats), or viscous liquids (oils).
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glycerol (alohol) stearic acid (fatty acid) tristearate (tristearin) a triglyceride 6.4.2 Physical properties of fats and oils
glyceryl
The most abundant unsaturated acids in fats and oils contain 18 carbon atoms. In all of these naturally occurring unsaturated acids, the configuration about C=C is cis. Fats are solid; oils are liquid at room temperature Fats contain a larger portion of saturated fatty acids whereas oils contain greater amounts of unsaturated fatty acids. Polyunsaturated means that each molecule of fat contains several C=C. Fats come from animal sources: Lard from hogs, tallow from cattle and sheep Oils come from vegetable sources: Olives, corn, peanut, soybean, canola In the unsaturated lipid, a cis double bond places a kink in the side chain, making it more difficult to pack efficiently in the solid state, thus leading to a lower melting point like oils.
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Oils derived from fish such as salmon, herring, mackerel, and sardines are very rich in polyunsaturated triacylglycerols. These triacylglycerols pack so poorly that they have very low melting points, and they remain liquids even in very cold water. Fish oils derived from omega-3 fatty acids are thought to be especially beneficial for individuals at risk for developing coronary artery disease.
Hardening Oils Hardening a fat or oil means to increase its melting point. Oils can be hardened by reducing the number of double bonds in the fatty acid part of the molecule. This is done by adding hydrogen a process called hydrogenation. When the double bond is removed the molecules can pack more tightly which increases the strength of the Van der Waals forces between the molecules. When margarine is prepared from vegetable oils the extent of hydrogenation is carefully controlled to make it easy to spread. Saturated fats are thought to less healthy than unsaturated fats being linked to heart disease. H2 + -CH=CHCH2-CH26.4.3 Soaps and detergents In the broadest sense possible, a detergent is simply a cleansing agent. Triglycerides can be broken apart under basic conditions (a saponification reaction) to produce long-chain carboxylate salts. Unlike their carboxylic acid forms, the carboxylate salts are at least somewhat soluble in water. Like all esters, fats and oils can be hydrolyzed (broken down by reaction with acid, base or enzymes). The products of
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hydrolyzing a fat and oils are propane-1,2,3-triol (glycerol) and a mixture of fatty acids. Hydrolysis can be accomplished by boiling the fat/oil with either a strong acid or a strong alkali. The alkaline hydrolysis is the more efficient method as it is non-reversible. When a fat is hydrolyzed using an alkali, such as sodium hydroxide, the products are propane-1,2,3-triol and a mixture of the sodium salts of the fatty acids.
glyceryl tristearate (tristearin) Carboxylate salt) glycerol a triglyceride
Sodium stearate (a a soap
A soap is distinguished from a synthetic detergent on the basis of chemical composition and not on the basis of function or usage. The one great advantage of synthetic detergents have over soap is that their Ca+2, Mg+2, and Fe+3 salts, as well as their Na+1 salts, are soluble in water. Therefore, they are nearly as effective in hard water as in soft water. The molecule of a nonionic (synthetic) detergent contains a grease-soluble component and a water soluble component. Some of these substances are especially useful in automatic washing machines because they have good detergent properties.
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CH3(CH2)10CH2-O-(CH2CH2O)7-CH2CH2OH Salts of fatty acids characteristics: a long, nonpolar, water-insoluble (hydrophobic) hydrocarbon tail. a charged, water-soluble (hydrophilic) head. When these substances are placed in water, their tails become tangled, thereby dissolving each other, leaving the charged, hydrophilic portions sticking out into the solution, allowing the whole micelle to dissolve in water, acting as a soap. Hydrophobic Hydrophilic combine two different solubility
water-insoluble (hydrophobic) non polar water-soluble (hydrophilic) - polar Organic substances that are readily decomposed by microorganisms in the environment are said to be biodegradable. Detergents that contain straight-chain alkyl groups are biodegradable. Biodegradable detergent
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NonBiodegradable detergent Some Important lipids Trimyristin Found in nutmeg, a spice obtained from the seed of the nutmeg tree, found in Indonesia and the West Indies, and other tropical areas.
Tristearin One of the principle compounds in beef fat and cocoa butter; triglycerides such as this lubricate meat fibers, and make the meat more tender when cooked; the yellow color of beef fat comes from carotene dissolved in tristearin.
Olestra A substitute for dietary fats developed by Procter & Gamble after 30 years and $200 million dollars worth of research; it is a combination of sucrose and fatty acids obtained from soybean oil and cottonseed oil; it is too hindered for digestive enzymes to react with; can carry small amounts of fat-soluble vitamins out of intestinal tract.
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Review questions 1. What is a carboxyl group? Ans: It is a carbonyl group attached to a hydroxyl group. 2. Is the following sentence true or false? Carboxylic acids are weak acids. Ans: True 3. What ending is used under the IUPAC system to designate a carboxylic acid? Ans: -oic acid
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4. Carboxylic acids with three or more carbons in a straight chain are also known ________ acids. Ans: fatty 5. What form do all aromatic carboxylic acids have at room temperature? Ans: crystalline solids 6. An ester is a derivative of a _______________ that has an OR substituted for the OH. Ans: Carboxylic acids 7. Write the general formula for an ester. ________ Ans: RCOOR 8. What two products are formed when an ester is hydrolyzed in the presence of a strong acid or base? Ans: It breaks down to form a carboxylic acid and an alcohol. 9. Draw structural formulas for: a. 2-methylhexanoic acid b. 8-bromooctanoic acid c. 2-chloro-6-methylheptanoic acid d, 4-decenoic acid e. 4,5-heptadienoic acid Ans: (a) (b)
(c)
(d)
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(e)
10. Draw structural formulas for: a. methyl acetate b. propyl hexanoate c. butyl pentanoate d. pentyl butanoate Ans: (a)
(b)
(c)
(d)
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11. Rank the fatty acids in each group in order of increasing melting point. a. CH3(CH2)14COOH, CH3(CH2)3CH=CH(CH2)7COOH, CH3(CH2)12COOH b. CH3(CH2)16COOH, CH3(CH2)7CH=CH(CH2)7COOH, CH3(CH2)5CH=CH(CH2)7COOH Ans: a. CH3(CH2)3CH CH(CH2)7COOH, CH3(CH2)12COOH, CH3(CH2)14COOH b. CH3(CH2)5CH CH(CH2)7COOH, CH3(CH2)7CH CH(CH2)7COOH, CH3(CH2)16COOH 12. How does each of the following affect the melting point of a fatty acid: (a) increasing the number of carbon atoms; (b) increasing the number of double bonds? Ans: a. Increasing the number of carbon atoms increases the melting point. b. Increasing the number of double bonds decreases the melting point. 13. Consider the following four types of compounds: [1] fatty acids; [2] soaps; [3] waxes; [4] triacylglycerols. For each type of compound: (a) give the general structure; (b) draw the structure of a specific example; (c) label the compound as water soluble or water insoluble; (d) label the compound as soluble or insoluble in the organic solvent hexane [CH3(CH2)4CH3]. Ans:
47
14. Answer the following triacylglycerol.
questions
about
the
given
a. What fatty acids are used to form this triacylglycerol? b. Would you expect this triacylglycerol to be a solid or a liquid at room temperature? c. What regions are hydrophobic? d. What regions are hydrophilic? Ans: a. arachidic acid, stearic acid, and lauric acid
48
b. solid c. The long hydrocarbon chains are hydrophobic. d. The ester linkages are hydrophilic. Give a derived and IUPAC name for the following carboxylic acids in the following 6 questions (15-20). 15. CH3(CH2)4COOH (caproic acid) Ans: n-Butylacetic acid, Hexanoic acid (6 C's in longest chain) 16. (CH3)3CCOOH (pivalic acid) Ans: Trimethylacetic acid, Dimethylpropanoic acid (3 C's in longest chain)
2,2-
17. (CH3)2CHCH2CH2COOH ( -methylvaleric acid) Ans: Isobutylacetic acid, 4Methylpentanoic acid
18. C6H5CH2CH2COOH phenylpropionic acid) Ans: Benzylacetic acid, Phenylpropanoic acid
( 3-
19. (CH3)2C(OH)COOH ( -hydroxyisobutyric acid) Ans: Dimethylhydroxyacetic acid,
49
2-Hydroxy-2-methylpropanoic acid
20. HOOC(CH2)2COOH (succinic acid) (no derived name) Ans: Butanedioic acid Name the following aromatic carboxylic acids questions (21-24) 21. Ans: p-nitrobenzoic acid
22.
Ans: 3,5-dibromobenzoic acid
23.
acid (COOH CHO. wherefore this compound is acid, not as an aldehyde)
Ans: takes
-formylbenzoic priority over named as an
24.
Ans: o-methylbenzoic acid, but more commonly called o-toluic acid (from toluene)
50
25. Account for the following physical properties of carboxylic acids, (a) Only RCOOH's with five or fewer C's are soluble in water, but many with six or more C's dissolve in alcohols, (b) Acetic acid in the vapor state has a molecular weight of 120 not 60. (c) Their boiling and melting points are higher than those of corresponding alcohols. Ans: (a) RCOOH dissolves because the H of COOH can H-bond with H20. The R portion is nonpolar and hydrophobic; this effect predominates as R gets large (over five C's). Alcohols are less polar than water and are less antagonistic toward the less polar carboxylic acids of higher C content. (b) CH3COOH typically undergoes dimeric intermolecular Hbonding.
(c) The intermolecular forces are greater for carboxylic acids. 26. Explain why highly branched carboxylic acids such as the one below are less acidic than unbranched acids. Ans: The C02- group of the branched acid is shielded from solvent molecules and cannot be stabilized by salvation as effectively as can acetateanion. 27. Use the mechanism of esterification to explain the lower rates of both esterification and hydrolysis of esters when the alcohol, the acid, or both have branched substiruent groups. Ans: The carbonyl C of RCOOH and RCOOR' is trigonal sp2hybridized, but that of the intermediate is tetrahedral sp3hybridized. If R' in R'OH or R in RCOOH is extensively branched,
51
formation of the unavoidably crowded transition state has to occur with greater difficulty and more slowly. 28. Write a formula for a fat (found in butter) of butanoic acid. Ans:
29. Alkaline hydrolysis of a fat of a high-molecular-weight acid gives a carboxylate salt (a soap). Write the equation for the reactions of the fat of palmitic acid, n-C15H31COOH, with aqueous NaOH. Ans:
Soap 30. Write two methods to prepare carboxylic acids? Ans: Oxidation of primary alcohols and aldehydes
Oxidative cleavage of alkenes and alkynes
52
31. Write the structural formula of Oxalic acid and explain the effects of it on human kidneys. Ans: It is found in many leafy green plants such as rhubarb and spinach; combines with calcium ions in the body to produce insoluble salts, which form kidney stones.
32. Fatty acids are ___________with long carbon chains of ________ carbon atoms. Ans: carboxylic acids (RCOOH), 1220 33. What is the difference between hydrophobic and hydrophilic? Ans: The nonpolar part of the molecule (comprised of C-C and C-H bonds) is not attracted to water, so it is said to be hydrophobic (water fearing). The polar part of the molecule is attracted to water, so it is said to be hydrophilic (water loving). 34. When ________ are combined with alcohols in the presence of an acid catalyst they react to form ________ and ________. Ans: carboxylic acids, esters and water 35. Write two physical properties of Esters. Ans: 1. Esters cannot hydrogen bond to each other and therefore have lower boiling points than carboxylic acids. 2. Esters can hydrogen bond to water and have appreciable water solubility. 36. What does it mean by saponification?
53
Ans: Saponification is the hydrolysis of an ester by a strong base (NaOH or KOH) to produce an alcohol and a salt (or soap if the salt formed is from a high-molar-mass acid). 37.
Write the above chemical equation in terms of words. Ans: acetic acid + ethanol ethyl acetate + water 38. What is the chemical name for Aspirin? Show its structural formula. Ans: acetylsalicylic acid
39. Fats and oils belong to a group of biological substances called________. Ans: lipids 40. Long-chain carboxylic acids, often referred to as fatty acids, are stored by living organisms by combining them with glycerol to produce tri-esters called _________. Ans: triglycerides 41. What does the word hydrogenation imply? Ans: Hydrogenation is the process of adding hydrogen to a chemical compound. Hardening a fat or oil will increase its melting point and is achieved by hydrogenation, which intern will reduce the number of double bonds. 42. Draw a structure for a soap and show the hydrophilic and hydrophobic part of it. Ans:
54
water-insoluble (hydrophobic) water-soluble (hydrophilic) - polar
non
polar
55

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6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Aliphatic carboxylic acids

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Solution Find and name the longest chain containing COOH.

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

3,3-dimethylcyclohexanecarboxylic acid (Notice that CO H as a substituent makes the carbon it is bound

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Ortho-hydroxybenzoic acid Example Name the following dicarboxylic acid

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6| Carboxylic acids, Esters, Fats and Oils

3-bromohexanedioic acid butanedioic acid

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Table 6.1 Common and IUPAC names of dioic (dicarboxylic) acids.

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Carboxylic acids also form hydrogen bonds to water molecules: H

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

acid + alcohol ester + water

permanganate can be used but gives lower yields.

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

Chemistry for Grades 11 & 12

6| Carboxylic acids, Esters, Fats and Oils

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6| Carboxylic acids, Esters, Fats and Oils

vinyl acetate (ethenyl ethanoate)

Chemistry for Grades 11 & 12