Chapter 05 2SPP

Chapter 5 Carboxylic Acids and Esters
Chapter 5
Carboxylic Acids and Esters
Chapter Objectives:
• Learn to recognize the carboxylic acid, ester, and related functional groups.
• Learn the IUPAC system for naming carboxylic acids and esters.
• 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
predict the products of ester synthesis and hydrolysis reactions.
• Learn some of the important properties of condensation polymers, especially the
polyesters.
Mr. Kevin A. Boudreaux

Angelo State University
CHEM 2353 Fundamentals of Organic Chemistry
Organic and Biochemistry for Today (Seager & Slabaugh)
www.angelo.edu/faculty/kboudrea
Carboxylic Acids
• Carboxylic acids are weak organic acids which
contain the carboxyl group (RCO2H):
O
O C O H
RCOOH RCO2H
O condensed ways of
R C OH writing the carboxyl
a carboxylic acid group
C H
O
the carboxyl group
• The tart flavor of sour-tasting foods is often caused

by the presence of carboxylic acids.
2
Nomenclature of
Carboxylic Acids
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
usual way.
• Aromatic carboxylic acids (i.e., with a CO2H
directly connected to a benzene ring) are named
after the parent compound, benzoic acid.
O
C
OH
4
Benzoic acid
Examples: Naming Carboxylic Acids

• Name the following compounds:
O O
H C OH CH3 C OH
O O
HO CCH2CH2CH3 CH3CH2 C OH

O
Br O
C OH
CH3CHCH2 C OH
CH3CH2CHCH3
CH3 O
CH3CHCH2 C OH
CH2CH2CH3
6

C OH CH3 O
CH3CCH3 CH3 CH C OH
CH2CH2CHCH3

CH3
CO2H
O
C OH
O
Cl
CH3 C OH
CH3CHCH3 8
More Complicated Acids

• For molecules with two carboxylic acid groups the
carbon chain in between the two carboxyl groups
(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
acid substituents.
O O
O O
HO C C OH
ethanedioic acid HO C CH2 CH CH2 C OH
O O C
O OH
HO C CH2 C OH propane-1,2,3-tricarboxylic acid
propanedioic acid 9
Examples: Drawing Carboxylic Acids

• Draw structural formulas for the following molecules:
– 2-methylpropanoic acid
– 2,2,5-trimethylhexanoic acid
– 4,5-dimethyl-3-nitrooctanoic acid
10
Examples: Drawing Carboxylic Acids

– para-bromobenzoic acid
– 2,4,6-trinitrobenzoic acid
– 4-ethylpentanedioic acid (what’s wrong with this name?)
11
12
Physical Properties of
Carboxylic Acids
13
Physical Properties of Carboxylic Acids

• Carboxylic acids hydrogen bond to themselves to
form a dimer:
O H O
R C C R
O H O
• Carboxylic acids also form hydrogen bonds to

water molecules: H
H O
O
R C
H
O H O
14
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.
15

• As the number of carbons in a carboxylic acid series
becomes greater, the boiling point increases and the
solubility in water decreases.
• 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.) 16
Table 5.2 Physical properties of some carboxylic acids

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 CH3(CH2)8—CO2H 270 32 Insoluble
Lauric acid CH3(CH2)10—CO2H 299 44 Insoluble
Myristic acid CH3(CH2)12—CO2H Dec. 58 Insoluble
Palmitic acid CH3(CH2)14—CO2H Dec. 63 Insoluble
Stearic acid CH3(CH2)16—CO2H Dec. 71 Insoluble
17
Boiling Points of Various Functional Groups
Figure 5.4
The boiling points of
carboxylic acids compared
to 1° alcohols, aldehydes
and ketones, ethers and
alkanes.
18
Comparing Physical Properties

Boiling Point: Water Solubility:
Carboxylic acid Carboxylic acid
Alcohols Alcohols
Aldehydes/Ketones Aldehydes/Ketones
Ethers Ethers
Alkanes Alkanes
Name Molecular Boiling Solubility in water

weight point
Pentane 72 g/mol 35°C Insoluble
Diethyl ether 74 g/mol 35°C Insoluble
Butanal 72 g/mol 76°C 7.1 g / 100 mL H2O
1-Butanol 74 g/mol 118°C 9.1 g / 100 mL H2O
Propanoic acid 74 g/mol 141°C Infinite 19
Examples: Predicting Physical Properties

• Arrange the following compounds in order of
increasing boiling point. (All of the compounds
have about the same molecular weight.)
– 1-pentanol
– hexane
– butanoic acid
– pentanal
• Which member of each of the following pairs of
compounds would you expect to have a higher
solubility in water?
– 2-butanone or propanoic acid
– hexanoic acid or ethanoic acid
20
Some Important
Carboxylic Acids
21
Important Carboxylic Acids

O
O O
CH3 CH3CH2 C OH
H C OH 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
the oxidation of ethanol) and
sourdough bread
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
22
O
O OH O
OH
HO OH
O OH H2N
2-hydroxy-1,2,3-propanetricarboxylic acid para-Aminobenzoic aid (PABA)

(Citric acid) Used in sunscreens; absorbs
Found in citrus fruits (lemons, grapefruit, short-wavelength UV light. It is also required
oranges, etc.); commonly used in buffering by bacteria for the production of folic acid,
solutions with sodium citrate 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
O O the bacteria from multiplying
HO OH O O
Oxalic acid
Found in many leafy green plants
such as rhubarb and spinach; HO OH
combines with calcium ions in the Terephthalic acid
body to produce insoluble salts, A white, crystalline solid; used in
which form kidney stones the manufacture of some
polyesters 23
O
HO
OH O
Glycolic acid
An alpha-hydroxy acid used in OH
cosmetics and skin creams;
alpha-hydroxy acids are thought to OH
loosen the cells of the epidermis and 2-hydroxypropanoic acid
accelerate the flaking off of dead skin; (Lactic acid)
however these compounds can increase Produced from the fermentation of sugars
the skin's sensitivity to UV light under anaerobic conditions; found in sweat,
sour milk, fermented pickles, sauerkraut,
and yogurt; produced in muscles from
glucose under anaerobic conditions (the
O
buildup of lactic acid leads to a heavy, weak
HO feeling, and muscle cramps); produced after
OH death during the breakdown of sugars in the
body by bacteria, inactivating the enzymes
O OH that allow the transport of calcium ions,
Malic acid causing rigor mortis
Responsible for the sharp
taste of apples (genus Malus)
24
O OH O
HO
OH OH
O OH
N
Niacin Tartaric acid
A water-soluble, B-Complex vitamin obtained Found naturally in wine, and is
from fish, green vegetables, lean meat, poultry, responsible for some of the sharp taste of
whole-grain and enriched bread and cereal; wine; it is added to many sour-tasting
produced in the body from tryptophan; sweet foods. The potassium salt, cream
essential for growth, healthy tissues, the of tartar, has many cooking applications;
production of energy from carbohydrates, and the potassium-sodium salt, Rochelle salt,
the production of fats is a mild laxative.
O O
HO HO
OH OH
O O
Succinic acid Fumaric acid

An intermediate along the Occurs naturally in many plants, and is essential for
citric acid cycle vegetable and animal tissue respiration; used in baking
powders, and in some fruit drinks as a replacement for
citric acid 25
H2N
OH
Gamma-aminobutanoic acid (GABA)
A inhibitory neurotransmitter; ethanol binds to the same
protein as GABA at a neighboring location, distorting the
protein so that GABA binds more easily, further inhibiting the
cell from firing; benzodiazepines such as Valium also bind to
the same protein but at a different site, inhibiting the cell still
further, and sometimes with deadly consequences
O O O O
HO N OH HO O- Na+
OH H NH2
Monosodium Glutamate (MSG)
Pantothenic acid The sodium salt of the amino acid glutamate;
A water-soluble B-complex vitamin; produced in meat during the decomposition of
converted by the body into proteins; with inosine monophosphate (IMP), one
Coenzyme A, which helps the body of the major substances responsible for the flavor
produce energy from food of meat; MSG is also added to some foods to
enhance their meaty flavor
26
Chemical Properties of
Carboxylic Acids
27
Acids and Bases

• Acids:
– have a sour taste.
– react with active metals to produce H2 gas.
– turn blue litmus red.
• Bases:
– have a bitter taste and a slippery feel.
– turn red litmus blue.
• When they react with each other, acids and bases
cancel each others properties in a neutralization
reaction:
acid + base  salt + water
28
Acids
• An acid gives a proton (H+) to another species.
Acids produce hydronium ions, H3O+, when they
are dissolved in water:
H—A + H2O  A– + H3O+
• A strong acid is one that completely dissociates in

water (i.e., every molecule of the acid splits apart):
H—Cl + H2O  Cl– + H3O+
• A weak acid is one in which only a small

percentage of the molecules are dissociated at any
one time (in other words, there is also a backwards
reaction, where the acid molecule is regenerated):
H—F + H2O h F– + H3O+
29
The pH Scale
• The acidity of a solution is measured
using the pH scale. The pH of a
solution is defined as
pH = - log[H3O+]
Acidic: pH < 7.00 [H3O+] > [OH-]
Basic: pH > 7.00 [H3O+] < [OH-]
Neutral: pH = 7.00 [H3O+] = [OH-]
30
The Acidity of Carboxylic Acids

• Carboxylic acids are weak acids; in water, they
dissociate to produce hydronium ions and
carboxylate ions:
O O
R C OH + H2O R C O + H3O
carboxylic acid carboxylate ion
• A 1.0 M solution of acetic acid is about 0.5%

dissociated into hydronium and acetate ions:
O O
CH3 C OH + H2O CH3 C O + H3O

acetic acid acetate ion
31
The Acidity of Carboxylic Acids

• The dissociation of a carboxylic acid is a reversible
reaction, and the position of the equilibrium can be
affected by the addition of acid (low pH) or by
adding base (high pH):
O base O
(high pH)
R C + H2O R C + H 3O
acid
O H (low pH) O
• At the physiological pH of 7.4 (the pH of most body

fluids) the carboxylate form of most carboxylic acids
is the predominate form.
32
Carboxylate Salts
33
Carboxylate Salts
• 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.
O O
R C OH + NaOH R C O- Na+ + H2O

carboxylic acid base metal carboxylate
O O
CH3 C O- Na+ CH3CH2CH2CH2 C O- NH4+

sodium ethanoate
(sodium acetate) 34
Examples: Carboxylate Salts

• Draw the structure of pyruvate, the form of pyruvic
acid which is found as an intermediate in energy
conversion reactions in living organisms.
O O
CH3 C C OH
pyruvic acid
• Complete the following reactions and name the

carboxylate salt products.
O
CH3 C OH + NaOH
O CH3
HO C CH2CHCH3 + NaOH 35
Examples: Carboxylate Salts

• Complete the following reactions and name the
carboxylate salt products.
O
C
OH
+ NaOH
C
OH
+ KOH
CH3
36
Physical Properties of Carboxylate Salts

• Carboxylate salts are ionic compounds, and are
typically solids at room temperature.
• Because they contain charges, carboxylate salts are
typically much more soluble in water than the
carboxylic acids from which they are derived.
– This is important in the formation of soaps (more
later).
O O
CH3(CH2)16C OH + NaOH CH3(CH2)16C O- Na+ + H2O

Stearic acid Sodium stearate
(octadecanoic acid) (sodium octadecanoate)
insoluble in water soluble in water
found in beef fat and
some butters
37
Important Carboxylate Salts

O O O OH O
O- Na+ + - - +
O- Na+ Na O O Na
Sodium propanoate - +
O O Na
O Sodium citrate
Sodium benzoate The sodium salt of citric acid, sodium citrate, is
Found in cranberries and
O- Ca2+ used in buffers with citric acid to maintain
prunes; commonly used desirable characteristics of foams and gels (jelly,
2
as a preservative in ice cream, candy, whipped cream, etc.) by
baked goods, ketchup, Calcium propanoate
controlling the pH of the product; also used in
carbonated beverages, Commonly used medicines and blood for transfusions; also
etc. preservatives; found functions as an anticoagulant in blood
in bread, cakes, and
cheeses
CH3 O
O C2H5
+ -
N O
N
C2H5
CH3 H
O
Denatonium benzoate ('Bitrex')
Benzyl diethyl ((2,6-xylylcarbamoyl)methyl) ammonium
O- Zn2+
Zinc 10-undecylenate 2 benzoate
Used to treat athlete's foot (Desenex) Discovered in 1958, this is the bitterest-tasting compound
known; as little as ten parts 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. 38
Esters
39
Esters
• An ester (“carboxylic ester” in the textbook) is a
derivative of a carboxylic acid in which there is a
carbon group connected to the single-bonded
oxygen:
O O
R C O R' R C O C
ester linkage carbon group
40
Nomenclature of Esters
O
R C O R'
acid part alcohol part
• Name the alkyl or aromatic portion contributed by

the “alcohol part” first.
• The “acid part” is named as a carboxylic acid, with
the -ic acid suffix changed to -ate.
O O
CH3 C O CH3 CH3CH2CH2 C O CH2CH3
41
Examples: Ester Nomenclature

CH3 O O
CH3 CH C O CH3 H C O CH3
O CH2CH3
CH3CH2 O C CH2CH2CHCH3
42

O CH3
CH3CH2CH C O CHCH3
CH2CH3
C O CH2CH3
43

CH3CH2CH2 C O
CH3
O
C O CH3
44
Examples: Drawing Esters

– methyl butanoate
– ethyl 2-methylpropanoate
– methyl 2,4-dimethylhexanoate
45
Examples: Drawing Esters

– propyl 2,2,3,4-tetramethylhexanoate
– isopropyl benzoate
– methyl para-nitrobenzoate
46
Some Important Esters
47
Important Esters
HO OH O
H
OH O
O Amyl acetate
O
OH Also known as banana oil and pear oil; the
commercially available compound is a
Vitamin C (ascorbic acid)
mixture of amyl (pentyl) isomers
A water-soluble vitamin found in citrus
fruits; prevents scurvy; essential for healthy
blood vessels, bones, and teeth; helps
form collagen, a protein that holds tissues O CH3 CH3
together +
O N
O CH3
O O– Acetylcholine
O N an important neurotransmitter
O
Peroxyacetyl nitrate (PAN) O
Produced by the action of sunlight on
fragments of unburnt hydrocarbon fuel,
oxygen, and nitrogen dioxide; one of the O
irritants (lachrymator) found in Benzyl acetate
photochemical smog oil of jasmine 48
OH O O
O O
Geranyl acetate
Coumarin geranium oil
Found in lavender
oil, sweet clover
and tonka beans O
O O
Warfarin
A potent rodenticide CH3(CH2)14 O(CH2)15CH3
O
Spermaceti
Also known as cetyl palmitate; found in
OCH3 the spermaceti organ or case above the
skull of the sperm whale (Physeter
macrocephalus). Its exact function is not
OH known but it may be used as
Methyl salicylate "cushioning," allowing the whale's head to
Also known as oil of wintergreen and betula be used as a battering ram in fights
oil; used as a flavoring and as an ingredient between males (see Moby Dick), as a
in deep heating rubs. It also fluoresces under regulator of the whale's buoyancy in
ultraviolet light, producing visible blue light. water, or as an aid in echolocation in
This is most apparent in Wint-O-Green focusing sound waves. Spermaceti was
Lifesavers, which contain methyl salicylate highly sought by whalers in the 18th and
as their flavoring. It is also used in some 19th centuries, and was widely used
commercially. 49
sunscreen lotions
Polymers with Ester Groups

O O O
O O O
Methyl acrylate (vinyl
C acetate)
Polymerizes to form polyvinyl Methyl methacrylate
N Polymerizes to form
acetate; used in acrylic paints
Methyl cyanoacrylate in combination with pigments poly(methyl methacrylate);
Polymerizes on contact with and a surfactant which causes trade names are Lucite,
surfaces containing trace the polymer to be suspended in Plexiglass, and Perspex;
amounts of water and an emulsion; also used in the bulky methyl and methyl
alcohols to form Superglue; safety glass (a layer of PVA ester groups cause the
superglue is also used in sandwiched between two polymer to be oriented
surgery in place of sutures, layers of glass) and chewing chaotically within the solid
and by morticians to seal gum polymer, allowing light to
the eyes and lips of their pass through without
clients scattering, rendering the
plastic transparent
O Lauryl methacrylate
Used to make the polymer poly(lauryl
methacrylate); used as an additive in
O viscostatic engine oils, which keeps
the oild viscous at high temperatures.
50
Reactions of Esters
51
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).
O O
+
H
C H + H O R' C R' + H O H

R O an alcohol R O
a carboxylic or
acid a phenol an ester
52

• 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.
O O O
C C C
R Cl R O R
acid chloride acid anhydride
53

O O
C + HO R' C R' + H Cl
R Cl R O
acid chloride an alcohol an ester
or
a phenol
O O O O
C C + HO R' C R' + C H
R O R an alcohol
R O R O
acid anhydride or an ester a carboxylic
a phenol acid
54
Examples: Esterification Reactions

• Write both products of the following reactions:
O
H+
CH3CH2CH2 C OH + CH3CH2OH
O
OH
CH3 C Cl +
55

O O
CH3 C O C CH3 + CH3CH2OH
56

O OH
CH3 C Cl + CH3 CH CH3
57

O
C O O
OH
+ CH3 C O C CH3
OH
58
Pain, Pain, Go Away

O O
OH OH
O
OH O
Salicylic acid CH3
Found in the bark of the willow
tree (Salix); a tea brewed from Aspirin (acetylsalicylic acid)
the bark reduces fever and Produced by reacting salicylic acid with acetic
relives pain and inflammation, anhydride, giving a compound which is less
but is very acidic, and causes acidic, and does not cause as much irritation,
irritation of the mucous but still retains all of the beneficial medical
membranes in the mouth, throat, properties; aspirin seems to work by blocking
and stomach, and can cause the production of prostaglandins, hormones
painful ulcers and stomach which may be responsible for producing pain,
bleeding fever and inflammation; one of the most
commonly used pharmaceutical drugs; over 40
million pounds are produced in the United
States per year
59
More Pain Relievers

O O
HN CH3 OH
OH OH
CH3O
Acetominophen
Does not cause stomach Naproxen
irritation, and has Ibuprofen An analgesic, anti-pyretic,
analgesic and antipyretic An analgesic, antipyretic, and anti-inflammatory
properties that are similar and anti-inflammatory drug; active ingredient in
to aspirin, but no drug; it is also not Aleve
anti-inflammatory irritating to the stomach
functions; available under lining; available under the
the trade names Tylenol, trade names Motrin,
Excedrin Aspirin Free, Advil, Ibuprin, Nuprin, and
Panadol, and Anacin-3 Mediprin
60
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 (Nylon, Ch. 6), form when each of the
monomers contain two of the same functional group,
so the reaction can take place at both ends.
61

O O
HOCH2CH2OH C C HOCH2CH2OH
Ethylene glycol HO OH Ethylene glycol
Terephthalic acid
O O
C C
HOCH2CH2O OCH2CH2OH
O O O O O O
C C C C C C
HO OCH2CH2O OCH2CH2O OH
O O O O O O
C C C C C C
HOCH2CH2O OCH2CH2O OCH2CH2O OCH2CH2OH
O O O O O O O O O O
C C C C C C C C C C
HO OCH2CH2O OCH2CH2O OCH2CH2O OCH2CH2O OH
etc.
62

O O
C C
H O O CH2CH2 OH
n
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.
63
Reactions of Esters: Ester Hydrolysis

• Esters may be broken apart under acidic conditions
by water (a hydrolysis reaction) to form a
carboxylic acid and an alcohol.
O O
+
H
R C OR' + H2O R C OH + R'OH
an ester a carboxylic acid an alcohol
• This is essentially the reverse reaction of the

synthesis of esters from carboxylic acids and
alcohols.
64
Reactions of Esters: Saponification

• Esters may be broken apart under basic conditions
by sodium hydroxide (lye) or potassium hydroxide
to form carboxylate salts and alcohols.
O O
R C OR' + NaOH R C O- Na+ + R'OH

an ester base a carboxylate salt an alcohol
• This reaction is important in the production of

soaps.
65
Examples: Splitting Esters

(Because Breaking Up Is Hard To Do)
• Complete the following reactions:

O
H+
CH3 C OCH2CH3 + H2O
CH3 C OCH2CH3 + NaOH
66
Triglycerides and Soaps
67
Triglycerides
• 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).
O
CH2 OH O CH2 OC(CH2)16CH3
O
CH OH HO C(CH2)16CH3
CH OC(CH2)16CH3
CH2 OH stearic acid O
(a fatty acid)
glycerol CH2 OC(CH2)16CH3
glyceryl tristearate (tristearin)
68
a triglyceride
Some Saturated Fatty Acids

O
OH
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
O
OH
Lauric acid
Found in coconut oil;
commonly used in soaps
O
OH
Myristic acid
A fatty acid found in butterfat,
coconut oil, and nutmeg oil
O
OH
Arachidic acid 69
A fatty acid found in peanut oil
Some Saturated Fatty Acids

O
OH
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 34°C (just
below body temperature); the sudden melting of chocolate in the
mouth gives it a pleasant feeling of coolness
70
Some Unsaturated Fatty Acids

O
OH
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
O
OH
Linolenic acid
A omega-6 polyunsaturated fatty acid found in linseed oil and corn oil
O
OH
Arachidonic acid
An omega-6 polyunsaturated fatty acid found in corn oil, linseed oil, animal tissues 71
Some Unsaturated Fatty Acids

O
OH
Eicosapentaenoic acid
A omega-3 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
OH
Palmitoleic acid
An unsaturated fatty acid found in butterfat and cod liver oil
OH
Docosahexaenoic acid
An omega-3 polyunsaturated fatty acid found in fish oil and seafoods
72
Triglycerides (Fats and Oils)

O
O O
O R
O
R O O R
O
O O O Triglycerides R
fats and oils (lipids)
C(CH2)12CH3 O R
O R
O
O
C(CH2)12CH3
O O
Tristearin C(CH2)16CH3
O
One of the principle O
C(CH2)12CH3
compounds in beef fat and O
O cocoa butter; triglycerides such
Trimyristin as this lubricate meat fibers, C(CH2)16CH3
Found in nutmeg, a spice and make the meat more O
obtained from the seed of tender when cooked; the
the nutmeg tree, found in yellow color of beef fat comes O
Indonesia and the West from carotene dissolved in C(CH2)16CH3
Indies, and other tropical tristearin.
areas O 73
O O
O
O
O
O
O
O O
O
O O
O
O
O
O
O
O
O
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 74
Saponification of Triglycerides
(Chewing the Fat)
• Triglycerides can be broken apart under basic
conditions (a saponification reaction) to produce
long-chain carboxylate salts.
O
CH2 OC(CH2)16CH3
O CH2 OH
O
NaOH
CH OC(CH2)16CH3 Na+ -O C(CH2)16CH3 CH OH
O Sodium stearate
a carboxylate salt CH2 OH
CH2 OC(CH2)16CH3
glycerol
glyceryl tristearate (tristearin)
a triglyceride
• Unlike their carboxylic acid forms, the carboxylate

salts are at least somewhat soluble in water.
75
Fatty Acid Salts

• Salts of fatty acids combine two different solubility
characteristics:
– a long, nonpolar, water-insoluble (hydrophobic)
hydrocarbon “tail.”
– a charged, water-soluble (hydrophilic) “head.”
O
O- Na+
Nonpolar, hydrophobic tail Polar, hydrophilic head
(water insoluble) CO2-
(water soluble)
• 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. 76
Soap
(Cleanliness, As They Say, Is Next To Impossible)
CO2-
Grease
77
a soap micelle
Soaps and Detergents O
O- Na+
Sodium stearate
O
O- 2Ca2+
Calcium stearate
"soap scum"
Sodium Alkylbenzenesulfonate
a synthetic detergent
SO3- Na+
Sodium para-Dodecylbenzenesulfonate
a biodegradable detergent
SO3- Na+
OH
O
Polyoxyethylene 78
A nonionic synthetic detergent; causes less foaming.
Esters of Inorganic
Acids
79
Esters of Inorganic Acids

O O
H+
R O H HO P OH RO P OH
an alcohol
OH OH
phosphoric acid a phosphate ester
(monoester)
R OH
O O
R OH
RO P OR RO P OH
OR OR
a phosphate triester a phosphate diester
80
Some Important Phosphate Esters

O O O O
CH2O P O-
RO P O P O P O-
O-
O
O- O- O-
OH
a phosphate triester NH2
HO OH
OH N
glucose-6-phosphate
N
Adenine
O O O
N N
- CH2
O P O P O P O
O
O- O- O- Ribose
Adenosine TriPhosphate (ATP)
OH OH 81
NH2
N
N
adenine
O
N N
-
O P O CH2 NH2
O
-
O deoxyribose
N
cytosine
O
- O N
O P O CH2 O
O
O
N
HN
guanine
O
H2N N
- N
O P O CH2 O
O
O CH3
HN
thymine
O
-
O N
O P O CH2
Deoxyribonucleic Acid O
O
(DNA)
82
OH
Reactions of Carboxylic Acids

1. Reaction of a carboxylic acid with water to form a carboxylate ion.
O O
+
R C + H2O R C + H3O
O H O-
2. Reaction of a carboxylic acid with a base to form a carboxylate salt and water.
O O
R C + NaOH R C + H2O
- +
O H O Na
carboxylic acid carboxylate salt
3. Reaction of a carboxylic acid with an alcohol to produce an ester and water.

O O
H+
C H + H O R' C R' + H O H
R O  R O
alcohol
carboxylic acid or phenol ester
4. Reaction of an acid chloride with an alcohol to produce an ester and HCl.

O O
C + H O R' C R' + H Cl
R Cl alcohol R O
ester 83
acid chloride or phenol
5. Reaction of an acid anhydride with an alcohol to produce an ester and a carboxylic acid.
O O O O
C C + H O R' C R' + C H
R O R alcohol R O R O
acid anhydride or phenol ester carboxylic acid
6. Hydrolysis of an ester to produce a carboxylic acid and an alcohol.

O O
H+
C R' + H2O C H + H O R'
R O  R O alcohol
ester carboxylic acid
7. Saponification of an ester to produce a carboxylate salt and an alcohol.

O O
C R' + NaOH C + H O R'
R O R O- Na+ alcohol
ester carboxylate salt
8. Formation of a phosphate monoester.

O O
+
H
HO P OH + R O H RO P OH + H2O
alcohol
OH OH
phosphoric acid phosphate monoester 84

Chapter 05 2SPP

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Chapter 5 Carboxylic Acids and Esters

Mr. Kevin A. Boudreaux

• The tart flavor of sour-tasting foods is often caused

Nomenclature of Carboxylic Acids

Examples: Naming Carboxylic Acids

Examples: Naming Carboxylic Acids

Examples: Naming Carboxylic Acids

Examples: Naming Carboxylic Acids

More Complicated Acids

Examples: Drawing Carboxylic Acids

Examples: Drawing Carboxylic Acids

– 4-ethylpentanedioic acid (what’s wrong with this name?)

Physical Properties of Carboxylic Acids

• Carboxylic acids also form hydrogen bonds to

Physical Properties of Carboxylic Acids

Physical Properties of Carboxylic Acids

Table 5.2 Physical properties of some carboxylic acids

Boiling Points of Various Functional Groups

Comparing Physical Properties

Name Molecular Boiling Solubility in water

Examples: Predicting Physical Properties

Important Carboxylic Acids

2-hydroxy-1,2,3-propanetricarboxylic acid para-Aminobenzoic aid (PABA)

Succinic acid Fumaric acid

Acids and Bases

• A strong acid is one that completely dissociates in

• A weak acid is one in which only a small

Acidic: pH < 7.00 [H3O+] > [OH-]

Basic: pH > 7.00 [H3O+] < [OH-]

Neutral: pH = 7.00 [H3O+] = [OH-]

The Acidity of Carboxylic Acids

• A 1.0 M solution of acetic acid is about 0.5%

CH3 C OH + H2O CH3 C O + H3O

The Acidity of Carboxylic Acids

• At the physiological pH of 7.4 (the pH of most body

R C OH + NaOH R C O- Na+ + H2O

CH3 C O- Na+ CH3CH2CH2CH2 C O- NH4+

Examples: Carboxylate Salts

• Complete the following reactions and name the

Examples: Carboxylate Salts

Physical Properties of Carboxylate Salts

CH3(CH2)16C OH + NaOH CH3(CH2)16C O- Na+ + H2O

Important Carboxylate Salts

acid part alcohol part

• Name the alkyl or aromatic portion contributed by

CH3 C O CH3 CH3CH2CH2 C O CH2CH3

Examples: Ester Nomenclature

CH3 CH C O CH3 H C O CH3

Examples: Ester Nomenclature

Examples: Ester Nomenclature

Examples: Drawing Esters

Examples: Drawing Esters

Some Important Esters

Polymers with Ester Groups

Synthesis of Esters: Esterification Reactions

Synthesis of Esters: Esterification Reactions

Synthesis of Esters: Esterification Reactions

Examples: Esterification Reactions

Examples: Esterification Reactions