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

O C O H
RCOOH RCO2H
Chapter Objectives: condensed ways of
R C OH O
• Learn to recognize the carboxylic acid, ester, and related functional groups. writing the carboxyl
• Learn the IUPAC system for naming carboxylic acids and esters. a carboxylic acid group
• Learn the important physical properties of the carboxylic acids and esters.
C H
• 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.
Nomenclature of • Name the substituents attached to the chain in the
usual way.
Carboxylic Acids • 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

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
H C OH CH3 C OH C OH
CH3CHCH2 C OH
CH3CH2CHCH3

O O

HO CCH2CH2CH3 CH3CH2 C OH
CH3 O

CH3CHCH2 C OH

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:
CH3
CO2H
O
O
CH3 O
C OH
C OH
CH3CCH3 CH3 CH C OH
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
HO C C OH – 4,5-dimethyl-3-nitrooctanoic acid
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 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

R C C R

Physical Properties of
O H O

Carboxylic Acids
• Carboxylic acids also form hydrogen bonds to
water molecules: H

H O
O

R C
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
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 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 CH3(CH2)8—CO2H 270 32 Insoluble Figure 5.4
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 CH3(CH2)14—CO2H Dec. 63 Insoluble and ketones, ethers and
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 Carboxylic acid increasing boiling point. (All of the compounds
have about the same molecular weight.)
Alcohols Alcohols
Aldehydes/Ketones Aldehydes/Ketones – 1-pentanol
Ethers Ethers – hexane
Alkanes Alkanes – butanoic acid
Molecular Boiling Solubility in water – pentanal
Name 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
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

Some Important
of ants and caterpillars;
produced in the body when
methanol is consumed
as mold inhibitors
acetic acid dissolved in water;
acetic acid is also responsible
for the taste of sour wine (from
the oxidation of ethanol) and

Carboxylic Acids
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

21 22

O
O OH O O
OH HO
HO OH OH O

O OH H2N Glycolic acid

2-hydroxy-1,2,3-propanetricarboxylic acid
(Citric acid)
Found in citrus fruits (lemons, grapefruit,
oranges, etc.); commonly used in buffering
solutions with sodium citrate
O O
HO OH
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
para-Aminobenzoic aid (PABA)
Used in sunscreens; absorbs
short-wavelength UV light. It is also required
by bacteria for the 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
O O
HO OH
Terephthalic acid
A white, crystalline solid; used in
the manufacture of some
polyesters
An alpha-hydroxy acid used in
cosmetics and skin creams;
alpha-hydroxy acids are thought to
loosen the cells of the epidermis and
accelerate the flaking off of dead skin;
however these compounds can increase
the skin's sensitivity to UV light
O
HO
OH
O OH
Malic acid
Responsible for the sharp
taste of apples (genus Malus)
23
OH
OH
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
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. The potassium salt, cream further, and sometimes with deadly consequences
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 O O

O O HO N OH HO
-
O Na
+

HO HO OH H NH2
OH OH
Monosodium Glutamate (MSG)
O Pantothenic acid The sodium salt of the amino acid glutamate;
O
A water-soluble B-complex vitamin; produced in meat during the decomposition of
Succinic acid Fumaric acid converted by the body into proteins; with inosine monophosphate (IMP), one
An intermediate along the Occurs naturally in many plants, and is essential for Coenzyme A, which helps the body of the major substances responsible for the flavor
citric acid cycle vegetable and animal tissue respiration; used in baking produce energy from food of meat; MSG is also added to some foods to
powders, and in some fruit drinks as a replacement for
enhance their meaty flavor
citric acid 25 26

Acids and Bases

• Acids:
– have a sour taste.
– react with active metals to produce H2 gas.

Chemical Properties of
– turn blue litmus red.
• Bases:

Carboxylic Acids
– 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
27 28

Acids The pH Scale

• An acid gives a proton (H+)
to another species. • The acidity of a solution is measured
Acids produce hydronium ions, H3O+, when they using the pH scale. The pH of a
are dissolved in water: solution is defined as
H—A + H2O  A– + H3O+ pH = - log[H3O+]

• A strong acid is one that completely dissociates in

water (i.e., every molecule of the acid splits apart):
Acidic: pH < 7.00 [H3O+] > [OH-]
H—Cl + H2O  Cl– + H3O+
Basic: pH > 7.00 [H3O+] < [OH-]
• A weak acid is one in which only a small
percentage of the molecules are dissociated at any Neutral: pH = 7.00 [H3O+] = [OH-]
one time (in other words, there is also a backwards
reaction, where the acid molecule is regenerated):
H—F + H2O h F– + H3O+
29 30
Chapter 5 Carboxylic Acids and Esters

The Acidity of Carboxylic Acids The Acidity of Carboxylic Acids

• Carboxylic acids are weak acids; in water, they • The dissociation of a carboxylic acid is a reversible
dissociate to produce hydronium ions and reaction, and the position of the equilibrium can be
carboxylate ions: affected by the addition of acid (low pH) or by
adding base (high pH):
O O
O base O
R C OH + H2O R C O + H3O (high pH)
carboxylic acid carboxylate ion R C + H2O R C + H3O
acid
O H (low pH) O
• A 1.0 M solution of acetic acid is about 0.5%
carboxylic acid carboxylate ion
dissociated into hydronium and acetate ions:
O O
• At the physiological pH of 7.4 (the pH of most body
CH3 C OH + H2O CH3 C O + H3O fluids) the carboxylate form of most carboxylic acids
acetic acid acetate ion is the predominate form.
31 32

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.

Carboxylate Salts R
O

C OH + NaOH R
O

C O- Na+ + H2O
carboxylic acid base metal carboxylate

O O
- +
CH3 C O Na CH3CH2CH2CH2 C O- NH4+
sodium ethanoate
33 (sodium acetate) 34

Examples: Carboxylate Salts Examples: Carboxylate Salts

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

• Complete the following reactions and name the

carboxylate salt products. O
O
C
CH3 C OH + NaOH OH
+ KOH
O CH3
CH3
HO C CH2CHCH3 + NaOH 35 36
Chapter 5 Carboxylic Acids and Esters

Physical Properties of Carboxylate Salts Important Carboxylate Salts

O O OH O
• Carboxylate salts are ionic compounds, and are O

typically solids at room temperature. -

O Na
+
O Na
- + + -
Na O
-
O Na
+

Sodium propanoate
• Because they contain charges, carboxylate salts are Sodium benzoate
typically much more soluble in water than the Found in cranberries and
prunes; commonly used
carboxylic acids from which they are derived. as a preservative in
baked goods, ketchup,
carbonated beverages,
– This is important in the formation of soaps (more etc.
later).
O O- Na+
O Sodium citrate
The sodium salt of citric acid, sodium citrate, is
O Ca
- 2+ used in buffers with citric acid to maintain
desirable characteristics of foams and gels (jelly,
Calcium propanoate
2
ice cream, candy, whipped cream, etc.) by
controlling the pH of the product; also used in
Commonly used medicines and blood for transfusions; also
preservatives; found functions as an anticoagulant in blood
in bread, cakes, and
cheeses

CH3 O
O C2H5

O O N
N+ -
O
C2H5
CH3 H
CH3(CH2)16C OH + NaOH CH3(CH2)16C O- Na+ + H2O O
Denatonium benzoate ('Bitrex')
Benzyl diethyl ((2,6-xylylcarbamoyl)methyl) ammonium
Stearic acid Sodium stearate O- Zn2+
Zinc 10-undecylenate 2 benzoate
(octadecanoic acid) (sodium octadecanoate) 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
insoluble in water soluble in water unbearably bitter to most humans. It is used as an aversive
found in beef fat and agent, an additive that prevents accidental ingestion of a
toxic substance. It is used to denature ethanol, methanol,
some butters and rubbing alcohol, and well as solvents, paints, arnishes,
37 antifreeze, etc. 38

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

Esters R C O R' R C O C
ester linkage carbon group

39 40

Nomenclature of Esters Examples: Ester Nomenclature

O • Name the following compounds:
CH3 O O
R C O R'
CH3 CH C O CH3 H C O CH3
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 CH2CH3

O O CH3CH2 O C CH2CH2CHCH3

CH3 C O CH3 CH3CH2CH2 C O CH2CH3

41 42
Chapter 5 Carboxylic Acids and Esters

Examples: Ester Nomenclature Examples: Ester Nomenclature

• Name the following compounds: • Name the following compounds:

O CH3
O
CH3CH2CH C O CHCH3
CH3CH2CH2 C O
CH2CH3

CH3
O O
C O CH2CH3 C O CH3

43 44

Examples: Drawing Esters Examples: Drawing Esters

• Draw structural formulas for the following molecules: • Draw structural formulas for the following molecules:
– methyl butanoate – propyl 2,2,3,4-tetramethylhexanoate

– ethyl 2-methylpropanoate – isopropyl benzoate

– methyl 2,4-dimethylhexanoate – methyl para-nitrobenzoate

45 46

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

Some Important Esters

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
47 48
Chapter 5 Carboxylic Acids and Esters

O
Polymers with Ester Groups
OH O O O O O
O O
Geranyl acetate
Coumarin geranium oil
Found in lavender O O O
oil, sweet clover Methyl acrylate (vinyl
C acetate)
and tonka beans O Methyl methacrylate
O O Polymerizes to form polyvinyl
N Polymerizes to form
Warfarin acetate; used in acrylic paints
A potent rodenticide Methyl cyanoacrylate in combination with pigments poly(methyl methacrylate);
CH3(CH2)14 O(CH2)15CH3
O Polymerizes on contact with and a surfactant which causes trade names are Lucite,
Spermaceti surfaces containing trace the polymer to be suspended in Plexiglass, and Perspex;
Also known as cetyl palmitate; found in amounts of water and an emulsion; also used in the bulky methyl and methyl
OCH3 the spermaceti organ or case above the alcohols to form Superglue; safety glass (a layer of PVA ester groups cause the
skull of the sperm whale (Physeter superglue is also used in sandwiched between two polymer to be oriented
macrocephalus). Its exact function is not surgery in place of sutures, layers of glass) and chewing chaotically within the solid
OH known but it may be used as and by morticians to seal polymer, allowing light to
gum
Methyl salicylate "cushioning," allowing the whale's head to the eyes and lips of their pass through without
Also known as oil of wintergreen and betula be used as a battering ram in fights clients scattering, rendering the
oil; used as a flavoring and as an ingredient between males (see Moby Dick), as a plastic transparent
in deep heating rubs. It also fluoresces under regulator of the whale's buoyancy in
water, or as an aid in echolocation in O Lauryl methacrylate
ultraviolet light, producing visible blue light.
focusing sound waves. Spermaceti was Used to make the polymer poly(lauryl
This is most apparent in Wint-O-Green
highly sought by whalers in the 18th and methacrylate); used as an additive in
Lifesavers, which contain methyl salicylate
19th centuries, and was widely used O viscostatic engine oils, which keeps
as their flavoring. It is also used in some
commercially. 49 the oild viscous at high temperatures.
50
sunscreen lotions

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).

Reactions of Esters O

C H + H O R'
H+

O

C R' + H O H
R O an alcohol R O
a carboxylic or
acid a phenol an ester

51 52

Synthesis of Esters: Esterification Reactions Synthesis of Esters: Esterification Reactions

• Since this reaction is a reversible reaction, it often O O
reaches an equilibrium with a large amount of
unreacted starting material still present. C + HO R' C R' + H Cl
R Cl R O
• Better yields are obtained using either acid acid chloride an alcohol an ester
chlorides or acid anhydrides as starting materials. or
a phenol
These reactions are nonreversible.

O O O
O O O O
C C C
R Cl C C + HO R' C R' + C H
R O R R O
R O R an alcohol R O
acid chloride acid anhydride acid anhydride or an ester a carboxylic
a phenol acid

53 54
Chapter 5 Carboxylic Acids and Esters

Examples: Esterification Reactions Examples: Esterification Reactions

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

O
OH
CH3 C Cl +

55 56

Examples: Esterification Reactions Examples: Esterification Reactions

• Write both products of the following reactions: • Write both products of the following reactions:
O OH O

C O O
CH3 C Cl + CH3 CH CH3
OH
+ CH3 C O C CH3

OH

57 58

Pain, Pain, Go Away More Pain Relievers

O O
OH
OH
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
commonly used pharmaceutical drugs; over 40
O O
HN CH3 OH
OH
O
O
O
CH3
Aspirin (acetylsalicylic acid) OH OH
CH3O
Produced by reacting salicylic acid with acetic Acetominophen
anhydride, giving a compound which is less Does not cause stomach Naproxen
acidic, and does not cause as much irritation, irritation, and has Ibuprofen An analgesic, anti-pyretic,
but still retains all of the beneficial medical analgesic and antipyretic An analgesic, antipyretic, and anti-inflammatory
properties; aspirin seems to work by blocking properties that are similar and anti-inflammatory drug; active ingredient in
the production of prostaglandins, hormones to aspirin, but no drug; it is also not Aleve
which may be responsible for producing pain, anti-inflammatory irritating to the stomach
fever and inflammation; one of the most functions; available under lining; available under the
the trade names Tylenol, trade names Motrin,
million pounds are produced in the United Excedrin Aspirin Free, Advil, Ibuprin, Nuprin, and
States per year Panadol, and Anacin-3 Mediprin

59 60
Chapter 5 Carboxylic Acids and Esters

Condensation Polymers: Polyesters Condensation Polymers: Polyesters

O O

• Condensation polymers are polymers which form HOCH2CH2OH

Ethylene glycol
C C HOCH2CH2OH
Ethylene glycol
HO OH
with the loss of a small molecule (typically water or Terephthalic acid

HCl).
O O
• Condensation polymers, such as polyesters and C C

polyamides (Nylon, Ch. 6), form when each of the HOCH2CH2O OCH2CH2OH

monomers contain two of the same functional group,

so the reaction can take place at both ends. 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

61 etc.
62

Condensation Polymers: Polyesters Reactions of Esters: Ester Hydrolysis

• Esters may be broken apart under acidic conditions
O O by water (a hydrolysis reaction) to form a
C C carboxylic acid and an alcohol.
H O O CH2CH2 OH
n
Polyethylene terephthalate
(PET) O O
A polyester H+
R C OR' + H2O R C OH + R'OH
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 an ester a carboxylic acid an alcohol
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 • This is essentially the reverse reaction of the
also be forced through narrow slits to produce thin sheets or synthesis of esters from carboxylic acids and
ribbons known as Mylar; this form is used as the support alcohols.
medium in audio and video tape.

63 64

Reactions of Esters: Saponification Examples: Splitting Esters

(Because Breaking Up Is Hard To Do)
• Esters may be broken apart under basic conditions
by sodium hydroxide (lye) or potassium hydroxide • Complete the following reactions:
to form carboxylate salts and alcohols. O
H+
O O CH3 C OCH2CH3 + H2O

R C OR' + NaOH R C O- Na+ + R'OH

an ester base a carboxylate salt an alcohol
O

• This reaction is important in the production of CH3 C OCH2CH3 + NaOH

soaps.

65 66
Chapter 5 Carboxylic Acids and Esters

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).

Triglycerides and Soaps 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)
67 68
a triglyceride

Some Saturated Fatty Acids Some Saturated Fatty Acids

O
O
OH
Stearic acid OH
A saturated fatty acid found in lard, beef fat,
Palmitic acid
butterfat, cottonseed oil; the sodium salt, produced
A fatty acid, found in lard, beef fat, butterfat, and cottonseed oil;
by heating lard with sodium hydroxide, can be used
the triglycerides in cocoa butter have oleic acid attached to the
as a soap
central oxygen, with stearic acid or palmitic acid on the other
O
oxygens; this more regular composition gives cocoa butter a much
sharper melting point than is usually observed in fats, and
OH chocolate remains brittle almost up to its melting point of 34°C (just
Lauric acid below body temperature); the sudden melting of chocolate in the
Found in coconut oil; mouth gives it a pleasant feeling of coolness
commonly used in soaps
O

OH
Myristic acid
A fatty acid found in butterfat,
coconut oil, and nutmeg oil
O

OH
Arachidic acid 69 70
A fatty acid found in peanut oil

Some Unsaturated Fatty Acids Some Unsaturated Fatty Acids

O
O

OH
OH

Oleic acid
An unsaturated fatty acid; the chain is much less flexible than that of Eicosapentaenoic acid
stearic acid because of the double bond, and cannot pack as tightly, A omega-3 polyunsaturated fatty acid found in fish oil and seafoods; omega-3 fatty
so the triglycerides it forms are oils and not fats; found in olive oil, acids may, according to some studies, help to lower the risk of heart disease
cocoa butter and chocolate, beef fat, lard, and peanut oil
O O

OH OH

Palmitoleic acid
Linolenic acid An unsaturated fatty acid found in butterfat and cod liver oil
A omega-6 polyunsaturated fatty acid found in linseed oil and corn oil
O
O

OH
OH
Docosahexaenoic acid
An omega-3 polyunsaturated fatty acid found in fish oil and seafoods
Arachidonic acid
An omega-6 polyunsaturated fatty acid found in corn oil, linseed oil, animal tissues 71 72
Chapter 5 Carboxylic Acids and Esters

Triglycerides (Fats and Oils)

O

O O O O
O R
O
O O
R O O R O
O
O O
O O O O
O Triglycerides R O
fats and oils (lipids) O O
C(CH2)12CH3 O R O
O R
O
O O
O
O
C(CH2)12CH3 O
O O
O
Tristearin C(CH2)16CH3 O
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 Olestra
obtained from the seed of tender when cooked; the A substitute for dietary fats developed by Procter & Gamble after 30 years and
the nutmeg tree, found in $200 million dollars worth of research; it is a combination of sucrose and fatty acids
yellow color of beef fat comes O
Indonesia and the West obtained from soybean oil and cottonseed oil; it is too hindered for digestive
from carotene dissolved in C(CH2)16CH3
enzymes to react with; can carry small amounts of fat-soluble vitamins out of
Indies, and other tropical tristearin.
O 73
intestinal tract 74
areas

Saponification of Triglycerides Fatty Acid Salts

(Chewing the Fat)
• Triglycerides can be broken apart under basic • Salts of fatty acids combine two different solubility
conditions (a saponification reaction) to produce characteristics:
long-chain carboxylate salts. – a long, nonpolar, water-insoluble (hydrophobic)
O
hydrocarbon “tail.”
CH2 OC(CH2)16CH3 – a charged, water-soluble (hydrophilic) “head.”
O CH2 OH
O O
NaOH +-
CH OC(CH2)16CH3 Na O C(CH2)16CH3 CH OH
O- Na+
O Sodium stearate Nonpolar, hydrophobic tail Polar, hydrophilic head
a carboxylate salt CH2 OH (water insoluble) CO2-
(water soluble)
CH2 OC(CH2)16CH3
glycerol
glyceryl tristearate (tristearin) • When these substances are placed in water, their
a triglyceride “tails” become tangled, thereby dissolving each
other, leaving the charged, hydrophilic portions
• Unlike their carboxylic acid forms, the carboxylate sticking out into the solution, allowing the whole
salts are at least somewhat soluble in water. micelle to dissolve in water, acting as a soap.
75 76

Soap Soaps and Detergents O

(Cleanliness, As They Say, Is Next To Impossible)
O- Na+
Sodium stearate
O

O- 2Ca2+
Calcium stearate
"soap scum"

CO2-
Grease
Sodium Alkylbenzenesulfonate
a synthetic detergent
SO3- Na+

Sodium para-Dodecylbenzenesulfonate
a biodegradable detergent
SO3- Na+
OH
O
77
Polyoxyethylene 78
a soap micelle A nonionic synthetic detergent; causes less foaming.
Chapter 5 Carboxylic Acids and Esters

Esters of Inorganic Acids

O O
H+
R O H HO P OH RO P OH
an alcohol
OH OH

Esters of Inorganic
phosphoric acid a phosphate ester
(monoester)

Acids R OH

O O
R OH
RO P OR RO P OH

OR OR
a phosphate triester a phosphate diester
79 80

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

Reactions of Carboxylic Acids 5. Reaction of an acid anhydride with an alcohol to produce an ester and a carboxylic acid.
O O O O
1. Reaction of a carboxylic acid with water to form a carboxylate ion.
O O C C + H O R' C R' + C H
+ R O R alcohol R O R O
R C + H2O R C + H3O ester carboxylic acid
acid anhydride or phenol
O H O-
carboxylic acid carboxylate ion 6. Hydrolysis of an ester to produce a carboxylic acid and an alcohol.
O O
2. Reaction of a carboxylic acid with a base to form a carboxylate salt and water.
O O H+
C R' + H2O C H + H O R'
R O  R O
R C + NaOH R C + H2O alcohol
ester carboxylic acid
O H O- Na+
carboxylic acid carboxylate salt 7. Saponification of an ester to produce a carboxylate salt and an alcohol.
O O
3. Reaction of a carboxylic acid with an alcohol to produce an ester and water.
O O C R' + NaOH C + H O R'
H+ R O R O- Na+ alcohol
C H + H O R' C R' + H O H ester carboxylate salt
R O  R O
alcohol
carboxylic acid or phenol ester
8. Formation of a phosphate monoester.
O O
4. Reaction of an acid chloride with an alcohol to produce an ester and HCl.
H+
O O HO P OH + R O H RO P OH + H2O
alcohol
C + H O R' C R' + H Cl OH OH
R Cl alcohol R O phosphoric acid phosphate monoester
ester 83 84
acid chloride or phenol