1. Chapter 14
Carboxylic Acids and
Carboxylic Acid Derivatives
2. 1. Carboxylic acids
The carboxyl group consists of carbonyl and hydroxyl
groups attached to the same carbon.
carbonyl + hydroxyl = carboxyl
An aliphatic or aromatic group can be attached to the carboxyl
group.
3. 1. Carboxylic acids
The acyl group is a carboxyl group with either a hydroxyl or
alkoxy group.
If R is a hydroxyl group, the compound is a carboxylic acid.
If R is an alkoxy group, the compound is an ester.
4. 1. Carboxylic acids: boiling points
Intermolecular forces are
strong in carboxylic acids
due to
the high polarity of the
carboxyl group;
the presence of hydrogen-
bonding between
carboxylic acid molecules.
5. 1. Carboxylic acids: boiling points
When two hydrogen
bonds form between
two carboxylic acid
molecules, the result is
a dimer.
Dimer formation can
cause carboxylic acids
to seem to have double
their actual molecular
mass.
6. 1. Carboxylic acids: boiling points
Compare molecules with similar molar masses and different
functional groups:
7. 1. Carboxylic acids: boiling points
Boiling point (oC) vs. number
of carbons for acids,
alcohols, aldehydes, and
alkanes.
8. 1. Carboxylic acids: solubility
Lower molecular weight carboxylic acids are very soluble in
water.
Vinegar is a solution of ethanoic acid.
Solubility falls off as molecular weight increases.
Why?
Hexadecanoic acid is insoluble in water.
9. 1. Carboxylic acids: solubility
Solubility (g acid/g H2O)
vs. number of carbons for
saturated, unbranched-
chain carboxylic acids.
10. 1. Carboxylic acids: nomenclature
Determine the parent compound from the
longest chain that includes the carboxyl
carbon.
Number the chain so that the carboxyl
carbon is carbon 1.
Replace the –e ending with –oic acid.
Assign numbers to any remaining substituents.
11. 1. Carboxylic acids: nomenclature
Additional notes:
If two carboxyl groups are present use –dioic acid.
For cycloalkanes, add carboxylic acid to the name of
the cycloalkane.
For aromatic acids, the simplest acid is benzoic
acid.
If the acid group is attached to the aromatic ring, name after
benzoic acid.
If the acid group is not attached to the aromatic ring, name
after the longest chain, with a –phenyl substituent.
15. 1. Carboxylic acids
Is “alpha-hydroxy” an actual substance?
glycolic acid
lactic acid
tartaric acid
16. 1. Carboxylic acids
The last paragraph in the inset box on pages 460-461 of
your textbook states:
"For the time being, biodegradable plastics cannot outcompete their
nonbiodegradable counterparts. Future research and development
will be required to reduce the cost of commercial production and
fulfill the promise of an 'environmentally friendly' garbage bag.”
This statement gives the impression that there are no biodegradable
plastics available to consumers at a reasonable cost.
Compostable plastic bags
17. 1. Carboxylic acids: reactions
Preparation is by complete oxidation of primary alcohols or
oxidation of aldehydes.
1o alcohol aldehyde carboxylic acid
18. 1. Carboxylic acids: reactions
Carboxylic acids are proton donors and therefore react as
acids.
Carboxylic acids are weak acids, dissociating only slightly
in solution.
>95% <5%
19. 1. Carboxylic acids: reactions
When a strong base is added to a carboxylic (weak) acid,
water and salt are formed.
Although the carboxylic acid isn’t initially completely
dissociated, as H+ is removed by reaction with OH-, more
acid dissociates.
Remember le Chatelier’s principle?
When product (H+) is removed, the equilibrium shifts to make more
product (and less undissociated acid).
20. 1. Carboxylic acids: reactions
Acid-base reaction
carboxylic acid + strong base carboxylic acid salt + water
21. 1. Carboxylic acids: reactions
Naming salts of carboxylic acids
Name the carboxylic acid.
Replace the –ic acid ending with –ate.
Precede this name with the name of the cation.
Name the salts formed in the following reactions:
ethanoic acid + KOH
benzoic acid + LiOH
hexanoic acid + NaOH
pencast
22. 1. Carboxylic acids: reactions
Esterification is the formation of water and an ester from a
carboxylic acid and an alcohol.
More about this in the next section…
23. 2. Esters
Esters are carboxylic acid derivatives, in which the acidic
-H of the acid has been replaced by an alkyl or aryl group –
R.
carboxylic acid ester derivative
24. 2. Esters: properties
Esters
are slightly polar;
boil at about the same temperature as corresponding aldehydes and
ketones;
are somewhat soluble in water when they are small.
have pleasant aromas.
25. 2. Esters: nomenclature
Recall nomenclature of salts of carboxylic acids.
Name the carboxylic acid.
Replace the –ic acid ending with –ate.
Precede this name with the name of the cation.
Esters are named in the same way, except the alkyl or aryl
portion of the alcohol is used in place of the cation name.
Name the carboxylic acid.
Replace the –ic acid ending with –ate.
Precede this name with the name of the alkyl or aryl portion of the
alcohol.
27. 2. Esters: nomenclature
Draw the structures of the following esters.
propyl ethanoate
octyl decanoate
methyl methanoate
2-methylpropyl propanoate pencast
3-methylbutyl ethanoate
phenyl pentanoate
28. 2. Esters: reactions
Preparation of esters is by reaction of a carboxylic acid and
an alcohol to produce an ester and water.
This is a dehydration reaction. [water is lost]
Heat and a trace of acid catalyst (H+) are required.
The reaction produces an equilibrium mixture.
heat
29. 2. Esters: reactions
Show the esterification reaction that would produce butyl
propanoate.
pencast
30. 2. Esters: reactions
Esters can be synthesized starting from alcohols only.
An alcohol can be oxidized to an aldehyde, and further oxidized to a
carboxylic acid.
This carboxylic acid can undergo an esterification reaction with
another alcohol.
Name the required alcohols and show the necessary
reactions to produce
pentyl butanoate (apricots).
octyl ethanoate (oranges).
pencast
31. 2. Esters: reactions
Hydrolysis (hydration) of esters, when it is acid-catalyzed,
is the reverse of the esterification reaction.
H2O
ester carboxylic acid alcohol
32. 2. Esters: reactions
Hydrolysis of esters, when it is base-catalyzed, is called
saponification.
ester carboxylic acid salt alcohol
33. 2. Esters: reactions
The carboxylic acid that forms when the ester breaks up
reacts immediately with the base, forming the carboxylate
anion, associated with the cation of the base.
34. 2. Esters: reactions
What are the products of the following reactions?
+ H2O
pencast
+ H2O
+ H2O
+ H2O
36. 2. Esters: saponification
A soap (carboxylic acid salt)
has a nonpolar end that dissolves in nonpolar fats and oils, and a
polar end that dissolves in water.
forms groups of soap molecules called micelles that dissolve in
water and are washed away.
38. EXTRA CREDIT QUESTION
Radioactive isotopes of an element behave chemically in exactly
the same manner as the nonradioactive isotopes. As a result,
they can be used as tracers to investigate the details of chemical
reactions. A scientist is curious about the origin of the bridging
oxygen atom in an ester molecule. She has chosen to use the
radioactive isotope 18O to study the following reaction:
Design experiments using 18O that will demonstrate whether the
oxygen in the water molecule came from the –OH of the alcohol
or the –OH of the carboxylic acid.
Post your answer in the Journal for this module with tag = XC.
39. 3. Acid chlorides and acid anhydrides
Acid chlorides are carboxylic acid derivatives in which the
hydroxyl group, -OH, has been replaced by –Cl.
Naming
Name the corresponding carboxylic acid.
Replace the -oic acid ending with –oyl chloride.
41. 3. Acid chlorides and acid anhydrides
Name the following acid chlorides.
pencast
Draw structures for the following acid chlorides.
heptanoyl chloride
2-hydroxypropanoyl chloride
42. 3. Acid chlorides and acid anhydrides
Preparation of acid chlorides
PCl3 or
+ PCl5 or + inorganic products
SOCl2
The reagents PCl3, PCl5, and SOCl2 are inorganic acid chlorides
43. 3. Acid chlorides and acid anhydrides
PCl3, PCl5, and SOCl2 replace the hydroxyl group on the
acid with a chloride, by the following mechanism!
44. 3. Acid chlorides and acid anhydrides
Write an equation for the reaction of benzoic acid with
SOCl2 and name the organic product.
pencast
SOCl2
benzoyl chloride
45. 3. Acid chlorides and acid anhydrides
Acid anhydrides are two carboxylic acid molecules with a
water molecule removed.
+ H2O
46. 3. Acid chlorides and acid anhydrides
Acid anhydrides with identical acyl groups are symmetrical.
Symmetrical acid anhydrides are named after the acid from
which they are made, with the acid ending replaced with
anhydride.
The molecule above, made from two molecules of ethanoic acid, is
called ethanoic anhydride.
47. 3. Acid chlorides and acid anhydrides
Unsymmetrical anhydrides have two different acyl groups.
Unsymmetrical anhydrides are named using both parent
carboxylic acid names, in alphabetical order, followed by the
word anhydride.
The molecule above is called butanoic ethanoic anhydride.
48. 3. Acid chlorides and acid anhydrides
Name the following acid anhydrides.
pencast
49. 3. Acid chlorides and acid anhydrides
Acid anhydrides can be prepared from an acid chloride and
a carboxylate anion.
Direct reaction of the two parent carboxylic acids is usually not
possible.
acid chloride carboxylate anion acid anhydride
50. 3. Acid chlorides and acid anhydrides
Write equations for the synthesis of butanoic anhydride,
beginning with butanoic acid.
pencast
51. 3. Acid chlorides and acid anhydrides
Acid anhydrides react with water, if it is present, to produce
two carboxylic acids.
+ H2O
52. 3. Acid chlorides and acid anhydrides
What are the products of the hydrolysis of
ethanoic anhydride?
pencast
ethanoic methanoic anhydride?
53. 3. Acid chlorides and acid anhydrides
An acid anhydride can also react with an alcohol, in a
reaction analogous to hydrolysis.
Hydrolysis: products are two carboxylic acids.
Reaction with alcohol: products are an ester and an acid.
Hinweis der Redaktion
In alcohols, the polar hydroxyl group and its ability to hydrogen bond make small alcohols completely miscible with water. As the nonpolar alkyl chain of the alcohol gets larger, it is harder and harder for the polar –OH to provide enough interaction with water to get the entire nonpolar “tail” into solution.The same thing is going on with carboxylic acids; the carboxyl group is very polar and can hydrogen bond with water. As the molar mass increases, the nonpolar hydrocarbon “tail” is harder and harder for the carboxyl group to get into solution.
Note that “complete solubility” means the same thing as “miscible.”The graph applies only to straight-chain carboxylic acids with no multiple bonds.The carboxylic acids with one through four carbons are completely soluble in water. These are methanoic acid, ethanoic acid, propanoic acid, and butanoic acid.At 5 carbons and beyond, the solubility drops off rapidly; hexadecanoic acid, with a 16-carbon chain, is insoluble in water.
Many cream and lotion bottles say, “with alpha-hydroxy!” You may be remembering that, when we have an –OH on a compound that is not an alcohol, the –OH substituent is called hydroxy-. In non-IUPAC nomenclature, the carbon next to the carboxyl carbon is called the alpha carbon. [The carbon two over from the carboxyl carbon is called the beta carbon.] A carboxylic acid with a hydroxyl group on the alpha carbon is called an alpha hydroxy acid. So, when a product claims it contains “alpha hydroxy,” it is claiming to have a molecule-less substituent. The correct term is “alpha hydroxy acid.”
We have been using BioBags for quite some time, and they work just fine and are not prohibitively expensive, especially if you consider the environmental cost of regular plastic bags.
For pentyl butanoate: Begin with butanol and oxidize it to butanoic acid. React butanoic acid with pentanol and a trace of acid to produce pentyl butanoate.For octyl ethanoate:Begin with ethanol and oxidize it to ethanoic acid. React ethanoic acid with octanol and a trace of acid to produce octyl ethanoate.
1. ethanoic acid and propanol2. potassium hexanoate and propanol3. sodium pentanoate and methanol4. hexanoic acid and 2-pentanol
Old fashioned soap was made from animal fat and lye, the equivalent of triglycerides and strong base shown in this slide. A triglyceride is a molecule with three esters attached.Each of these three esters detaches in the presence of base to form a carboxylic acid salt. The other product is glycerol, properly called 1,2,3-propanetriol according to IUPAC rules. The salts of carboxylic acids act as soaps.