Ministry of Public Health of Ukraine

Ukrainian Medical Stomatological Academy

Department of biological and bioorganic chemistry

Carbonyl compound aldehydes, ketones, carboxylic acids

Assoc. Prof. Bilets M.V.

 Lecture plan

 The structure of the carbonyl group.

 Chemical properties of aldehydes.
 Chemical properties of ketones.
 Chemical properties of carboxylic acids.
 The structure of the carbonyl group.

 The carbonyl group is a functional

group composed of
a carbon atom double-bonded to
an oxygen atom: C=O.
 Carbonyl group C=O is present in The oxygen has two lone pairs of electrons hanging around.
aldehydes, ketones, and carboxylic These electrons make the oxygen more electronegative than
acids and their derivatives: carbon. The carbon is then partially postive (electrophillic) and
the oxygen partially negative (nucleophillic).

Compounds containing a carbonyl group have higher melting and

boiling points than hydrocarbons containing the same number of
carbon atoms and are more soluble in polar solvents such as
water. The carbonyl group can enter into a variety of
chemical reactions; nucleophilic reagents (electron-rich
reagents) are attracted to the carbon atom, whereas
http://www.qorganica.es/QOT/T9/carbonilicos_e_exported/in electrophilic reagents (electron-seeking reagents) are
dex.html
attracted to the oxygen atom.
https://www.spectroscopyonline.com/view/carbonyl-group-part-i-
introduction
 Aldehydes.

 The aldehyde is a compound containing a functional group with

the structure −CHO, consisting of a carbonyl center (a carbon
double-bonded to oxygen) with the carbon atom also bonded
to hydrogen and to any generic alkyl or side chain R group.
There are two general ways of naming aldehydes:
 The first method is based on the system used by the IUPAC and
is often referred to as systematic nomenclature. This method
assumes the longest chain of carbon atoms that contains the
carbonyl group as the parent alkane. The aldehyde is shown by
changing the suffix -e to -al. Because the carbonyl group of an
aldehyde can only be on the end of the parent chain and,
therefore, must be carbon 1, there is no need to use a number to
locate it.
 The other method of nomenclature for aldehydes, referred to as
common nomenclature, is to name them after the common
name of the corresponding carboxylic acid; i.e., the carboxylic
acid with the same structure as the aldehyde except that
―COOH appears instead of ―CHO. The acids are usually given
a name ending in -ic acid. Aldehydes are given the same name
but with the suffix -ic acid replaced by -aldehyde. Two examples
are formaldehyde and benzaldehyde.

https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_(Organic_Chemistry)/Aldehydes_a
nd_Ketones/Nomenclature_of_Aldehydes_and_Ketones
 Chemical properties of aldehydes.

Aldehydes are typically more reactive than ketones

due to the following factors:
 Aldehydes are less hindered than ketones (a hydrogen atom is smaller than any other
organic group).
 The carbonyl carbon in aldehydes generally has more partial positive charge than in
ketones due to the electron-donating nature of alkyl groups.
 Aldehydes only have one e- donor group while ketones have two.
 Oxidation-reduction reactions of aldehydes
 Fehling's test.
 The carbon atom of a carbonyl group has a relatively  This test helps to do detect the presence of carbohydrates in a
high oxidation state. The most common and solution (glucose in urine), because the carbohydrates having
characteristic oxidation reaction is the conversion of free or potentially free carbonyl groups (aldehyde or ketone) can
aldehydes to carboxylic acids: RCHO → RCOOH. act as reducing sugars.
 Aldehydes can be reduced to primary alcohols:  Fehling's solution and Benedict's solution are variants of essentially the
RCHO → RCH2OH. same thing. Both contain complexed copper(II) ions in an alkaline solution.

 Fehling's solution contains copper(II) ions complexed with tartrate ions in

 Useful tests for aldehydes, Tollens' test, Trommers’, sodium hydroxide solution. Complexing the copper(II) ions with tartrate
Fehling's test, take advantage of this ease of oxidation by ions prevents precipitation of copper(II) hydroxide.
using Ag(+) and Cu(2+) as oxidizing agents (oxidants).  Benedict's solution contains copper(II) ions complexed with citrate ions in
 Tollens’ test, also known as silver-mirror test, is a qualitative sodium carbonate solution. Again, complexing the copper(II) ions prevents
the formation of a precipitate - this time of copper(II) carbonate.
laboratory test used to distinguish between an aldehyde and a
ketone. It exploits the fact that aldehydes are readily oxidized.
whereas ketones are not. Tollens’ test uses a reagent known as
Tollens’ reagent, which is a colorless, basic, aqueous solution
containing silver ions coordinated to ammonia [Ag(NH3)2+] .

https://chem.libretexts.org/Courses/Brevard_College/CHE_202%3A_Organic_Chemistry_II
/01%3A_Aldehydes_and_Ketones/1.05%3A_Oxidation_of_Aldehydes_and_Ketones
 Reactions of nuclephilic addition (АN)

Nucleophilic addition of H2O Nucleophilic addition of alkohols

(formation of hemiacetal and acetal)

Nucleophilic addition of HCN

(formation of hydroxyalkanenitrile
(cyanohydrins))

ethanale 2-hydroxy-2-methylpropanenitrile

https://chem.libretexts.org/Courses/Athabasca_University/Chemistry_360%3A_Organic_Chemistry_II/Chapter_19%3A_Al
dehydes_and_Ketones%3A_Nucleophilic_Addition_Reactions
 The reaction of aldol condensation

 Aldol condensation reactions signify an

essential class of reactions for the
formation of carbon-carbon bonds. An
aldol reaction involves the condensation
of two carbonyl compounds to form a ß-
hydroxyaldehyde or ß-hydroxyketone,
the aldol product.

 The typical aldol reaction involves self

condensation of the reactant ketone or
aldehyde wherein one molecule adds to Aldolases there are enzymes that catalyses an aldol reaction
the other of the same type. An example (creating an aldol) or its reverse (cleaving an aldol), such as
of a self-condensation with acetaldehyde fructose-bisphosphate aldolase of glycolysis and
as the sole reactant. gluconeogenesis.

https://www.azom.com/article.aspx?ArticleID=8887
 The reaction of disproportionation (dismutation, Cannizzaro’s).

The Cannizzaro reaction, named after its discoverer Stanislao

Cannizzaro, is a chemical reaction that involves the base-
induced disproportionation of two molecules of a non- Formaldehyde is disproportionated to formic acid and methyl
enolizable aldehyde (formaldehyde and benzaldehyde): one molecule of alcohol.
aldehyde is reduced to the corresponding alcohol, while a second one
is oxidized to the carboxylic acid.

Benzaldehyde can be converted to benzoic acid and benzyl alcohol.

https://www.adichemistry.com/organic/namedreactions/cannizzaro/ca
nnizzaro-1.html
 Haloform reactions of aldehydes and ketones

The haloform reaction is the reaction of a methyl When the halogen used is iodine, the haloform reaction
ketone with chlorine, bromine, or iodine in the can be used to identify methyl ketones because iodoform
presence of hydroxide ions to give a carboxylate is a yellow solid with a characteristic odor. The test is
ion and a haloform. There is one aldehyde that known as the iodoform test. Alcohols also give a positive
iodoform test because, under the reaction conditions, they
undergoes the haloform reaction, which is
are oxidized to the corresponding methyl ketone, or, in
acetaldehyde. the case of ethanol to acetaldehyde, which is the only
aldehyde that undergoes haloform reaction.

https://chem.libretexts.org/Bookshelves/Ancillary_Materials/Reference/Organic_Chemistry_Glossary/Haloform_Reaction#:~:text=The%20haloform%20reaction%20is%20the,haloform%20react
ion%2C%20which%20is%20acetaldehyde.
 Ketones.

Ketones contain a carbonyl group linked to two Ketone derivatives are: - ketoses – monosaccharides such as
carbon-containing radicals: fructosab ribulose;
- steroid hormones (testosteron);
-purine, pyrimidine nitogenouse bases;
-Ketoacids (acetoacetic, oxalic, keto-glutaric) ets.
The simplest ketone is propanone or acetone
with the formula:  The IUPAC system of nomenclature assigns
a characteristic suffix of -one to ketones.

Acetone - one of the types of ketone bodies (they

also include acetoacetic and beta-hydroxybutyric
acids), is synthesized in the liver and serves as a
source of energy for the brain and muscles
(especially the myocardium). An increase in
blood concentration - ketonemia, is characteristic
of fasting, an insulin-dependent type of diabetes
mellitus.
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_(Organic_Chemistry)/Aldehydes_a
nd_Ketones/Nomenclature_of_Aldehydes_and_Ketones
 Chemical properties of ketones.

 Keto-enol tautomerization  C-H bonds adjacent to the carbonyl in ketones are more
acidic than the C-H bonds in alkane. The relative acidity of
 Ketones that have at least one alpha-hydrogen, the α-hydrogen is important in the enolization reactions of
undergo keto-enol tautomerization; the tautomer ketones and other carbonyl compounds. The acidity of the α-
is an enol. Tautomerization is catalyzed by both hydrogen also allows ketones and other carbonyl compounds
to react as nucleophiles at that position, with either
acids and bases. Usually, the keto form is more stoichiometric and catalytic base.
stable than the enol.
 Ketones are also weak bases, undergoing protonation on the
carbonyl oxygen in the presence of Brønsted acids.
 An aldehyde differs from a ketone in that it has a hydrogen
atom attached to its carbonyl group, making aldehydes easier
to oxidize. Ketones do not have a hydrogen atom bonded to
the carbonyl group, and are therefore more resistant to
oxidation. They are oxidized only by powerful oxidizing
agents which have the ability to cleave carbon–carbon
bonds.

https://www.chemistrylearner.com/keto-enol-tautomerism.html
 Carboxylic acids.

 A carboxylic acid is an organic acid that contains

a carboxyl group (COOH) attached to an R-group.
The general formula of a carboxylic acid is: Formula Common Name IUPAC Name
methanoic
HCOOH formic acid
acid
ethanoic
CH3COOH acetic acid
acid
 Carboxylic acids are commonly identified by their propionic propanoic
CH3CH2COOH
trivial names. They often have the suffix -ic acid. acid acid
IUPAC-recommended names also exist; in this
system, carboxylic acids have an -oic acid suffix. For CH3(CH2)2CO butanoic
example, butyric acid (C3H7CO2H) is butanoic acid butyric acid
OH acid
by IUPAC guidelines.
CH3(CH2)3CO pentanoic
valeric acid
 Carboxylic acids occur widely. Important examples OH acid
include the amino acids and fatty acids.
 Classification of carboxylic acids.

- According to the number of carboxyl groups, carboxylic acids are

divided into:
monocarboxylic (one -COOH group), dicarboxylic (two -COOH
groups), etc.

- Depending on the structure of the hydrocarbon radical to which the

carboxyl group is linked, carboxylic acids are:
aliphatic (for example, acetic or acrylic), alicyclic (for example,
cyclohexanecarboxylic), or aromatic (benzoic, phthalic).
 Examples of carboxylic acids

Acetic acid Citric, isocitric acids

Citric acid or Isocitric acid or1-
2-Hydroxypropane- Hydroxypropane-1,2,3-
Acetic acid (ethanoic acid) tricarboxylic acid:
1,2,3-tricarboxylic acid:

At physiological pH, acetic acid is usually fully ionised to

acetate.

The acetyl group, formally derived from acetic acid, is

fundamental to all forms of life. Derivate of acetic acid - Citric and isocitric acids are examples of
acetyl coenzyme A, (acetyl-CoA). It is acetic acid, binded tricarboxylic acids.
with coenzyme A. Acetyl-CoA is central metabolit of many Citratic and isocitric asids are intermediates
biochemical processes (Krebs cycle, synthesise of fatty acids,
cholesterol, metabolism of some amino acids, ets.). in the Tricarboxylic Acid cycle cycle (TCA,
or Krebs cycle), - central metabolic pathway.
 Examples of carboxylic acids

Succinic acid Malonic acid

Succinic acid (1,4-Butanedioic acid):
Malonic acid ( propanedioic acid):
HOOC-CH2- CH2-COOH HOOC-CH2-COOH
It is a dicarboxylic saturated acid. It is a dicarboxylic saturated acid.
The name comes from the Latin succinum, which means Malonic acid is the classic example of a competitive
amber. In living organisms, succinic acid takes the form of
an anion. Succinate is produced in mitochondria in the inhibitor of enzyme succinate dehydrogenase. Inhibition
tricarboxylic acid cycle. And then, in the same cycle, it is of this enzyme decreases cellular respiration and ATP
converted into fumarate by the enzyme succinate synthesis.
dehydrogenase. This enzyme is part of complex 2 of the Fumaric acid
electron transport chain, which is involved in the production
of ATP.
Fumaric acid (trans-1,2-Ethylenedicarboxylic acid,2-
Butenedioic acid):
HOOC-CH=CH-COOH
It is dicarboxylic unsaturated acid.
Fumaric aci is metabolit of Citric Acid cycle and Urea
cycle.
 Examples of carboxylic acids

Oxalic acid Glutaric acid

Oxalic acid (ethanedioic acid):

Glutaric acid (Propane-1,3-dicarboxylic acid 1,3-
HOOC-COOH Propanedicarboxylic acid, Pentanedioic acid, n-
It is a dicarboxylic acid . Pyrotartaric acid):
Oxalic acid is a competitive inhibitor of the enzyme HOOC-CH2- CH2-CH2-COOH
lactate dehydrogenase (LDH). LDH catalyzes the
reversible conversion of pyruvate to lactic acid (the
end product of anaerobic glycolysis). Glutaric acid is naturally produced in the body during
Oxalic acid salts - oxalates can cause kidney stones. the metabolism of some amino acids,
In addition, they enhance the crystallization of uriс including lysine and tryptophan. Defects in this
acid in the kidneys. Enters the body with food metabolic pathway can lead to a disorder
(tomatoes, grapes, citrus fruits) called glutaric aciduria, where toxic byproducts build
up and can cause severe encephalopathy.
 Chemical properties of carboxyl group.

The carboxyl (COOH) group is so-named because of

As a result, the bond between oxygen and hydrogen atoms in the
the carbonyl group (C=O) and hydroxyl group.
hydroxyl group becomes more polar and the hydrogen atom acquires
In the carboxyl group, everyone is polar. The carbon atom is
increased mobility, which greatly simplifies its separation in the form
in a state of sp2 hybridization. It forms three σ-bonds: two
of a proton (H +). As a result of the mutual influence of atoms in the
with oxygen atoms and one with a hydrogen atom in formic
carboxyl group, the C = O bond is stronger than in the carbonyl
acid or carbon in molecules of other carboxylic acids. σ-
group of aldehydes, and the O-H bond is less strong than in alcohols.
bonds are located in one plane, the angle between them is
The acidic properties of carboxylic acids are due to the shift of the
close to 120◦.
electron density to the carbonyl oxygen atom and the resulting
The carbon atom forms another bond with the oxygen atom
strong polarization of the O - H bond (in comparison with alcohols
of the carbonyl group. The unhybridized p-orbitals of the
and phenols), as a result of which the separation of the hydrogen
carbon atom and the carbonyl oxygen atom overlap to form a
atom in the form of a proton is facilitated. Carboxylic acids, unlike
π-bond.
alcohols, dissociate to form hydrogen ions H.
In the carbonyl group, the electron density is shifted towards
For carboxylic acids, in contrast to aldehydes, addition reactions at
the oxygen atom due to its high electronegativity. As a
the double bond> C = O are not characteristic, due to a decrease in
result, a partial positive charge arises on the carbonyl carbon
the positive charge on the carbonyl carbon atom by the oxygen atom
atom. The carbon atom seeks to compensate for the positive
of the hydroxo group.
charge and attracts the lone pair of electrons of the oxygen
atom of the hydroxyl group.
In turn, the oxygen atom pulls off the electron density along
the O-H bond from the hydrogen atom of the hydroxyl
group.
 Chemical properties of carboxylic acids.

Conversion of a Carboxylic Acid to an Amide

https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modul
es_(Organic_Chemistry)/Carboxylic_Acids/Reactivity_of_Carboxylic_Acids/Fischer_
Esterification

https://www.slideserve.com/taite/carboxylic-acids
 Chemical properties of carboxylic acids.

Esterification

Esterification is the esterification of a carboxylic

acid by heating it with an alcohol in the presence of a
strong acid as the catalyst.

https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_(Organic_Chemistry)/Carboxylic_A https://www.slideserve.com/taite/carboxylic-acids
cids/Reactivity_of_Carboxylic_Acids/Fischer_Esterification
 Sources of information

 https://www.adichemistry.com/organic/namedreactions/cannizzaro/cannizzaro-1.html
 https://chem.libretexts.org/Bookshelves/Ancillary_Materials/Reference/Organic_Chemistry_Glossary/Haloform_Reaction#:~:text=The%20haloform%20reaction%
20is%20the,haloform%20reaction%2C%20which%20is%20acetaldehyde.
 https://www.spectroscopyonline.com/view/carbonyl-group-part-i-introduction
 http://www.qorganica.es/QOT/T9/carbonilicos_e_exported/index.html
 https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_(Organic_Chemistry)/Aldehydes_and_Ketones/Nomenclature_of_Aldehydes_
and_Ketones
 https://chem.libretexts.org/Courses/Brevard_College/CHE_202%3A_Organic_Chemistry_II/01%3A_Aldehydes_and_Ketones/1.05%3A_Oxidation_of_Aldehydes
_and_Ketones
 https://chem.libretexts.org/Courses/Athabasca_University/Chemistry_360%3A_Organic_Chemistry_II/Chapter_19%3A_Aldehydes_and_Ketones%3A_Nucleophil
ic_Addition_Reactions
 https://www.azom.com/article.aspx?ArticleID=8887
 https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_(Organic_Chemistry)/Aldehydes_and_Ketones/Nomenclature_of_Aldehydes_
and_Ketones
 https://www.slideserve.com/taite/carboxylic-acids
 https://www.chemistrylearner.com/keto-enol-tautomerism.html
 https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_(Organic_Chemistry)/Carboxylic_Acids/Reactivity_of_Carboxylic_Acids/Fisc
her_Esterification
 Biological and Bioorganic Chemistry. In 2 books. Book 1. Bioorganic Chemistry.
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