Carboxylic acids, esters, and other acid derivatives

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Carboxylic acids, esters, and other acid
derivatives

• Chapter 16

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Structure of carboxylic acids and their
derivatives

• The functional group present in a carboxylic acid
  is a combination of a carbonyl group and a
  hydroxyl group however, the resulting carboxyl
  group ( -COOH) possesses properties that are
  unlike those present in aldehydes/ketones and
  alcohols.

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Structure of carboxylic acids and their
derivatives

• Carboxylic acids have the following general
  formula
• Some simple carboxylic acids
• Since carbon can have only four bonds, there are
  no cyclic carboxylic acids (i.e. the carboxyl
  group cannot form part of a carbon ring)

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Structure of carboxylic acids and their
derivatives

• The following molecules have a similar structure
  to carboxylic acids, and will be encountered in
  this chapter and the next.

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IUPAC nomenclature for carboxylic acids

• For monocarboxylic acids (one COOH group)
• Select the longest, continuous carbon chain that
  involves the carboxyl group. This is the parent
  chain and the COOH carbon is designated as C-1.
• Name the parent chain by dropping the e from
  the corresponding alkane name and changing to
  oic acid
• Indicate the identity and location of
  substituents on the parent chain at the front of
  the carboxylic acids name

Benzoic acid
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IUPAC nomenclature for carboxylic acids

• Dicarboxylic acids
• For these compounds, both ends of a chain will
  end with a COOH group. The parent chain is the
  one that involves both COOH groups.
• The parent chain is named as an alkane and the
  term dioic acid is added afterwards to indicate
  the diacid structure.

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Common names for carboxylic acids
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Common names for dicarboxylic acids
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Common names for carboxylic acids

• For common-name carboxylic acids and diacids,
  substituents are often numbered using a Greek
  system
• So the following molecule could be called
  a-Methylpropionic acid (or, using the IUPAC
  system, 2-Methylpropanoic acid)

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Polyfunctional carboxylic acids

• Carboxylic acids that contain other functional
  groups besides the COOH group are called
  polyfunctional carboxylic acids. Some examples
  are shown below

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Polyfunctional carboxylic acids
Unsaturated acids

• Unsaturated acids possess a unit of unsaturation
  (double/triple C-C bond) in the structure. Three
  of the most common unsaturated acids are shown

a metabolic acid
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Polyfunctional carboxylic acids
Hydroxy acids

• Four of the simplest hydroxy acids

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Polyfunctional carboxylic acids
Keto acids

• For keto acids, a carbonyl group is present as
  part of a carbon chain that involves a carboxyl
  group
• For IUPAC naming of this structure, the O-atom of
  the carbonyl group is treated as an oxo
  substituent and the molecule is called
  2-Oxopropanoic acid

Oxo-group
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Metabolic carboxylic acids

• Polyfunctional acids are intermediates in
  metabolic reactions that occur as food is
  processed to obtain energy.
• Eight key intermediates in these processes are
  derived from only three carboxylic acids
  (propanoic, butanoic, and pentanoic acids, see
  below)

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Physical properties of carboxylic acids

• Carboxylic acids are the most polar functional
  group we have seen so far. The presence of the
  carbonyl group next to the OH causes the O-H bond
  to be even more polar.

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Physical properties of carboxylic acids

• Because of the very polar COOH group, carboxylic
  acids exhibit strong intermolecular attractions.
• As expected, carboxylic acids of a given number
  of carbon atoms have higher boiling points than
  alcohols.
• Carboxylic acids also tend to dimerize, producing
  molecules that are twice as heavy which have
  enhanced London forces (and thus still higher
  boiling points).

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Physical properties of carboxylic acids

• In terms of water-solubility, because of
  H-bonding, carboxylic acids dissolve well in
  water (up to 4-carbon chains).
• Beyond 4 carbons, water-solubility drops off
  rapidly.

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Preparation of carboxylic acids

• We saw in Ch-15 that carboxylic acids can be
  prepared from aldehydes (which can be prepared
  from primary alcohols)
• Aromatic carboxylic acids can be made by
  oxidizing alkyl-substituted aromatic molecules

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Acidity of carboxylic acids

• When carboxylic acids are placed in water, they
  undergo de-protonation as discussed in Ch-10

Remember from Ch-10 HA H2O D A- H3O
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Acidity of carboxylic acids
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Acidity of carboxylic acids
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Carboxylic acid salts

• When carboxylic acids are reacted with strong
  bases, they are converted to salts as follows

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Carboxylic acid salts

• Salts of carboxylic acids are much more
  water-soluble than the acids themselves. Also,
  they can be converted back to the acid form by
  reacting them with a strong acid

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Uses of carboxylic acid salts

• Because of their enhanced solubility in water
  compared to the acid form, many drugs and
  medicines that possess acid groups are marketed
  as carboxylic acid salts (sodium or potassium
  salts).

frogurt
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Structure of esters

• Esters are carboxylic acid derivatives having an
  alkoxy group instead of a hydroxyl group.

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Preparation of esters

• Esters are prepared by condensation reactions
  involving carboxylic acids and alcohols. Such
  reactions are called esterification reactions
• This an ester consists of an acid portion and an
  alcohol portion

Reaction is encouraged by the presence of excess
alcohol (Le Chateliers Principle)
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Preparation of esters

• Cyclic esters (lactones) are created from hydroxy
  acids (bear both a hydroxyl group and a carboxyl
  group) in an intramolecular esterification
  reaction

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Preparation of esters

• Indicate the structures of the carboxylic acid
  and alcohol that are needed to make each of the
  following esters

H
carboxylic acid alcohol
ester
H2O
H
H2O
H
H2O
H
H2O
H
H2O
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Nomenclature for esters

• Thinking of an ester in terms of an alcohol
  portion and a carboxylic acid portion is
  important for naming esters using the IUPAC
  system
• The name for the alcohol portion comes first
  name the alkyl part of the alcohol (e.g., for the
  ester shown below, the first part of the esters
  name is methyl (alcohol part comes from
  methanol). Present the alkyl name separate from
  the remainder of the ester name.
• The carboxylic acid portion is named as if it
  were deprotonated, changing the -ic acid part
  of that name to -ate

Methyl propanoate
This part would be called propanoate
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Nomenclature for esters

• Some other examples

Ethyl butanoate
b
Ethyl 2-methylbutanoate Ethyl a-methylbutyrate
a
g
2-Methylpropyl butanoate Isobutyl butanoate
2-Butyl butanoate Sec-Butyl butanoate
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Selected common esters

• Flavor/fragrance agents

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Selected common esters

• Pheromones
• Medications

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Selected common esters

• Synthesis of Aspirin
• Synthesis of oil of wintergreen

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Isomerism in carboxylic acids and esters

• Recall that constitutional isomers are molecules
  that share the same formula but differ in their
  atom-to-atom connectivities.
• Three kinds of constitutional isomers (in the
  order we encountered them)
• positional isomers
• skeletal isomers
• functional group isomers
• Carboxylic acids and esters that have a given
  number of carbon atoms form another example of
  functional group isomers

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Isomerism in carboxylic acids and esters

• For both carboxylic acids and esters, skeletal
  isomers are possible

(carboxylic acids)
(esters)
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Isomerism in carboxylic acids and esters

• Positional isomers are possible for esters, but
  not carboxylic acids.

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Physical properties of esters

• Because they dont possess OH groups, esters
  cannot form H-bonds with other ester molecules.
  As a result, esters have lower boiling points
  than carboxylic acids and alcohols that have
  approximately the same molar mass.
• Water molecules can H-bond to esters, at the
  oxygen atoms. This makes low molecule weight
  esters water-soluble.

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Chemical reactions of esters

• Ester hydrolysis the hydrolysis of an ester is
  accomplished by reacting water with the ester in
  the presence of an acid catalyst (this is the
  reverse reaction of esterification).
• An example

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Chemical reactions of esters

• Ester saponification another hydrolysis
  reaction, but this time, under basic conditions.
  Rather than a carboxylic acid, the acid salt is
  produced here.
• Example

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Sulfur analogs of esters

• In Ch-14 and 15, we saw sulfur analogs of
  alcohols, ethers, aldehydes, and ketones. Esters
  also have known sulfur analogs, thioesters
• Thioesters are made by condensation reactions
  involving carboxylic acids and thiols.

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Sulfur analogs of esters

• Thioesters, like esters, have relatively low
  boiling points (compared to alcohols and
  carboxylic acids) and may be found in foods as
  flavorings.
• Acetyl coenzyme A, a thioester, is important in
  metabolic cycles that provide our bodies with
  energy.

Methyl thiobutanoate
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Polyesters

• In Ch-13, we saw how unsaturated molecules like
  ethylene can undergo addition polymerization.
• Condensation polymerization creates polymers
  through the loss of water molecules

Difunctional reactants
A polyester
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Polyesters

• Polyesters are very important materials for
  textiles (clothing, upholstery, etc.) and
  plastics.
• About 50 of PET production goes towards textiles
  and the other 50 towards plastics/materials for
  applications
• soda bottles
• audio/video tapes
• medicinal applications like heart valves and mesh
  for arterial replacements

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Polyesters

• Biodegradable polymers are also made by this
  route. Polyesters of lactic acid and glycolic
  acid are used to make the lactomer shown below,
  which undergoes hydrolysis after a few weeks to
  produce lactic acid and glycolic acid.
• Used as materials for sutures, this polymer
  enables dissolvable stiches which produce
  materials that are already present in the body.

Lactic acid
Glycolic acid
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Acid chlorides and acid anhydrides

• Acid chlorides and anhydrides have structures
  that are quite similar to carboxylic acids and
  esters.
• Both are able to be hydrolized to produce
  carbolxylic acids.
• Acid chlorides are produced by reaction of a
  carboxylic acid with an inorganic chloride (PCl3,
  PCl5, or SOCl2).

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Acid chlorides and acid anhydrides

• Acid chlorides are named as follows
• first as a carboxylic acid
• Remove the -ic acid and add -oyl chloride

Hydrolysis reaction
Esterification
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Acid chlorides and acid anhydrides

• Acid anhydrides are made by condensation
  reactions between carboxylic acids (or between
  acid chlorides and carboxylic acids)
• Naming is straightforward indicate the names of
  the acids used to make the anhydride (without the
  acid part included)

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Acid chlorides and acid anhydrides
Acyl transfer reactions

• Carboxylic acids (esters, acid chlorides)
  possess an acyl group (notice how this is
  different that the carboxyl group of the acid)
• Acyl transfer reactions occur during protein
  synthesis. The reaction involves the formation
  of a new bond between the acyl group and another
  molecular fragment.
• One example of an acyl transfer occurs during an
  esterification

Acyl group
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Esters and anhydrides of inorganic acids

• We have seen inorganic acids like H2SO4, H3PO4,
  and HNO3 in the first semester of this course.
  These can also react with alcohols to make
  inorganic esters

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Esters and anhydrides of inorganic acids

• Phosphate esters are the most important class of
  inorganic esters.
• Because phosphoric acid has three OH groups, it
  can form mono-, di- and tri-esters

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Esters and anhydrides of inorganic acids

• Phosphoric acid anhydrides are also made via
  condensation reactions
• These systems are important components of
  cellular processes for biochemical energy
  production.