Aldehydes

and Ketones

Chem 104
Carbonyl group
• Carbonyl group – consists of
a carbon atom bonded to an
oxygen atom by a double
bond
• Compounds containing a
carbonyl group are called
carbonyl compounds.
• This group includes the
aldehydes, ketones,
carboxylic acid, amide
Carbonyl groups
Aldehydes and Ketones
• Similar chemical and physical properties
• Distinguished by the location of the carbonyl group within the carbon
chain.
• In aldehydes the carbonyl group is always located at the end of the
carbon chain (carbon-1). In ketones the carbonyl group is located
within the carbon chain of the molecule.
• In ketones the carbonyl carbon is attached to two other carbon
atoms.
• In aldehydes the carbonyl carbon is attached to at least one
hydrogen atom; the second atom attached to the carbonyl carbon of
an aldehyde may be another hydrogen or a carbon atom
Structure and • Aldehydes and ketones are
Physical polar compounds because of
the polar carbonyl group
Properties • Because of the dipole-dipole
attractions between molecules,
they boil at higher temperatures
than hydrocarbons or ethers
that have the same number of
carbon atoms or are of
equivalent molecular weight.
 Structure and Physical Properties

• Because they cannot form intermolecular hydrogen bonds, their

boiling points are lower than those of alcohols of comparable
molecular weight.
Aldehydes and Ketones
• Aldehydes and ketones can form intermolecular
hydrogen bonds with water.
• As a result, the smaller members of the two
families (five or fewer carbon atoms) are
reasonably soluble in water.
• However, as the carbon chain length increases, the
compounds become less polar and more
hydrocarbon like.
• These larger compounds are soluble in nonpolar
organic solvents.
Exercise

• Which member in each

of the following pairs
will be more water
soluble?
Answers
 Exercise

• Which member in each of

the following pairs would
have a higher boiling
point?
Nomenclature and Common Names
Aldehydes
• Determine the parent compound, that is, the longest continuous
carbon chain containing the carbonyl group.
• Replace the final -e of the parent alkane with -al.
• Number the chain beginning with the carbonyl carbon (or
aldehyde group) as carbon-1.
• Number and name all substituents as usual.
• No number is used for the position of the carbonyl group
because it is always at the end of the parent chain. Therefore, it
must be carbon-1.
Nomenclature
and Common
Names
Nomenclature
and Common
Names
Common Names and Formulas for Several Aldehydes
Nomenclature of Aldehydes

• Greek letters are used

to indicate the position
of the substituents.
• The carbon atom
bonded to the carbonyl
group is the α-carbon,
the next is the β-
carbon, and so on.
Nomenclature of Aldehydes
Exercise
Exercise

• Use the I.U.P.A.C. and

common nomenclature
systems to name each
of the following
compounds.
Exercise
• Write the condensed
structural formula for each
of the following
compounds
Nomenclature of Ketones

• The rules for naming ketones are directly analogous to those for
naming aldehydes.
• In ketones, however, the -e ending of the parent alkane is
replaced with the -one suffix of the ketone family, and the
location of the carbonyl carbon is indicated with a number. The
longest carbon chain is numbered to give the carbonyl carbon
the lowest possible number.
Nomenclature of Ketones
Example
Common Nomenclature system to name
Ketones
• Common names of ketones are derived by naming the alkyl
groups that are bonded to the carbonyl carbon.
• These are used as prefixes followed by the word ketone.
• The alkyl groups may be arranged alphabetically or by size
(smaller to larger).
 Exercise
Use the IUPAC nomenclature
system to name each of the
following compounds:
Important Aldehydes and Ketones
Methanal (Formaldehyde)
• A GAS, BP -21oC
• Available commercially as an aqueous solution called formalin.
• Formalin has been used as a preservative for tissues and as an
embalming fluid.
Ethanal (acetaldehyde)
• produced from ethanol in the liver.
• Ethanol is oxidized in this reaction, which is catalyzed by the liver
enzyme alcohol dehydrogenase.
• The ethanal that is produced in this reaction is responsible for the
symptoms of a hangover
Important Aldehydes and Ketones
Propanone (acetone)
• simplest ketone, an important and versatile solvent for organic
compounds.
• ability to dissolve organic compounds and is also miscible with water.
• has a number of industrial applications and used as a solvent in
adhesives, paints, cleaning solvents, nail polish, and nail polish
remover.
• Propanone is flammable and should therefore be treated with
appropriate care.
Butanone
• a four-carbon ketone, is also an important industrial solvent.
Important Aldehydes and Ketones
• Many aldehydes and ketones are produced industrially as food
and fragrance chemicals, medicinals, and agricultural
chemicals.
• They are particularly important o the food industry, in which they
are used as artificial and/or natural additives to food.
• Vanillin, a principal component of natural vanilla
• Artificial vanilla flavoring is a dilute solution of synthetic vanillin
dissolved in ethanol
Important Aldehydes and Ketones
Important Aaldehydes and Ketoes
Important Aldehydes and Ketones
Reactions involving Aldehydes and
Ketones
Preparation of Aldehydes and Ketones
• Aldehydes and ketones are prepared by the oxidation of the
corresponding alcohol.
• The oxidation of methyl alcohol gives methanal (formaldehyde).
• The oxidation of a primary alcohol produces an aldehyde, and
the oxidation of a secondary alcohol yields a ketone.
• Tertiary alcohols do not undergo oxidation under the conditions
normally used.
 Reactions
involving
Aldehydes and
Ketones
Oxidation Reactions
• Aldehydes are easily oxidized further to carboxylic acids,
whereas ketones do not generally undergo further oxidation.
• Reason: an aldehydic carbon-hydrogen bond, present in the
aldehyde but not in the ketone, is needed for the reaction to
occur.
• In fact, aldehydes are so easily oxidized that it is often very
difficult to prepare them because they continue to react to give
the carboxylic acid rather than the desired aldehyde.
Oxidation Reactions
• Aldehydes are susceptible to air oxidation, even at room
temperature, and cannot be stored for long periods.
Oxidation Reactions

• Many oxidizing
agents can be used.
Both basic
potassium
permanganate and
chromic acid are
good oxidizing
agents
Oxidation of
Aldehyde
• The silver
precipitate produced
by the Tollens’
reaction is
deposited on glass.

• Silver mirrors are

made in a similar
process
Oxidation Reactions

• The oxidation of
benzaldehyde to
benzoic acid is an
example of the
conversion of an
aromatic aldehyde to
the corresponding
aromatic carboxylic
acid:
Oxidation Reactions
• Aldehydes and ketones can be distinguished on the basis of
differences in their reactivity.
• The most common laboratory test for aldehydes is the Tollens’
test. When exposed to the Tollens’ reagent, a basic solution of
Ag(NH3)2+, an aldehyde undergoes oxidation.
Oxidation Reactions
• The silver ion (Ag+) is reduced to silver metal (Ag0) as the
aldehyde is oxidized to a carboxylic acid anion.

• Silver metal precipitates from solution and coats the flask,

producing a smooth silver mirror,
Oxidation Reactions
• The test is therefore often called the Tollens’ silver mirror test.
The commercial manufacture of silver mirrors uses a similar
process.
• Ketones cannot be oxidized to carboxylic acids and do not react
with the Tollens’ reagent.
Oxidation Reactions
• Another test that is used to distinguish between aldehydes and
ketones is Benedict’s test.
• a buffered aqueous solution of copper(II) hydroxide and
sodium citrate reacts to oxidize aldehydes but does not
generally react with ketones.
• Cu2+ is reduced to Cu+ in the process. Cu2+ is soluble and gives
a blue solution, whereas the Cu+ precipitates as the red solid
copper(I) oxide, Cu2O.
Oxidation Reactions
• All simple sugars (monosaccharides) are either aldehydes or
ketones.
• Glucose is an aldehyde sugar that is commonly called blood
sugar because it is the sugar found transported in the blood and
used for energy by many cells. In uncontrolled diabetes,
glucose may be found in the urine.
• One means to determine the amount of glucose in the urine is
to use Benedict’s test and look for the color change.
• The amount of precipitate formed is directly proportional to the
amount of glucose in the urine
Oxidation
Reactions
Reaction of glucose
with the Benedict’s
reagent
Oxidation Reactions
• When the carbonyl group of a ketone is bonded to a —CH2OH
group, the molecule will give a positive Benedict’s test.
• This occurs because such ketones are converted to aldehydes
under basic conditions
• Ketone sugars are converted to aldehyde sugars and react with
Benedict’s reagent
Reduction reactions
• Aldehydes and ketones are both readily reduced to the
corresponding alcohol by a variety of reducing agents.
• The classical method of aldehyde or ketone reduction is
hydrogenation.
• The carbonyl compound is reacted with hydrogen gas and a
catalyst (nickel, platinum, or palladium metal) in a pressurized
reaction vessel. Heating may also be necessary.
• The carbon-oxygen double bond (the carbonyl group) is
reduced to a carbon-oxygen single bond.
Reduction reactions

• This reaction is
similar to the
reduction of an
alkene to an alkane
(the reduction of a
carbon-carbon
double bond to a
carbon-carbon
single bond). The
addition of hydrogen
to a carbon-oxygen
double bond is
shown
Reduction reactions

• The hydrogenation (reduction) of a ketone produces a secondary alcohol

Reduction reactions

• The hydrogenation of an aldehyde results in the production of a primary alcohol

Exercise
Answers
Addition Reactions
• The principal reaction of the carbonyl group is the addition
reaction across the polar carbon-oxygen bond.
• Such reactions require that a catalytic amount of acid be
present in solution
• An example of an addition reaction is the reaction of aldehydes
with alcohols in the presence of catalytic amounts of acid.
Addition Reactions
• The hydrogen of the alcohol adds to the carbonyl oxygen; the
alkoxyl group of the alcohol (—OR) adds to the carbonyl carbon
• The predicted product, having the structure just described,
is a hemiacetal.
Addition Reactions
• Hemiacetals are quite reactive. In the presence of acid and
excess alcohol, they undergo a substitution reaction in which
the —OH group of the hemiacetal is exchanged for another
—OR group from the alcohol. The product of this reaction is an
acetal. Acetal formation is a reversible reaction, as shown:
Addition Reactions
Consider the acid-catalyzed reaction between propanal and
methanol:
Addition Reactions
• Addition reactions will also occur between a ketone and an
alcohol.
• the more reactive intermediate is called a hemiketal and the
product is called a ketal. The general equation for ketal
formation is shown:
 Addition reactions

• A ketal is the final product in the reaction between propanone and

ethanol, seen in the following equation:
Hemiacetals and Hemiketals
• Readily formed in carbohydrates. Monosaccharides contain
several hydroxyl groups and one carbonyl group.
• The linear form of a monosaccharide quickly undergoes an
intramolecular reaction in solution to give a cyclic hemiacetal or
hemiketal
• hemiacetals and hemiketals formed in intermolecular reactions
are unstable and continue to react, forming acetals and ketals.
• This is not the case with the intramolecular reactions involving
five- or six-carbon sugars; the cyclic or ring form of the molecule
is more stable than the linear form.
 Hemiacel
formation in
Sugars
Hemiacetals and Hemiketals
• When the hemiacetal or hemiketal of one monosaccharide
reacts with a hydroxyl group of another monosaccharide, the
product is an acetal or a ketal.
• A sugar molecule made up of two monosaccharides is called a
disaccharide; the C—O—C bond between the two
monosaccharides is called a glycosidic bond
 • Acetal formation is demonstrated in the formation of the
disaccharide sucrose, common table sugar.
Glycosidic • The reaction between the hydroxyl groups of the
bond monosaccharides glucose and fructose produces the acetal
sucrose; the bond between the two sugars is a glycosidic
bond
Keto-enol tautomers
• Many aldehydes and ketones may exist in an equilibrium
mixture of two constitutional or structural isomers called
tautomers.
• Tautomers differ from one another in the placement of a
hydrogen atom and a double bond.
• One tautomer is the keto form (on the left in the equation
below). The keto form has the structure typical of an aldehyde
or ketone.
 Keto-enol tautomers

• The other form is called the enol form

• The enol form has a structure containing a carbon-carbon double bond (en) and a
hydroxyl group, the functional group characteristic of alcohols (ol).
• Because the keto form of most simple aldehydes and ketones is more stable, they
exist mainly in that form.
 • Phosphoenolpyruvate is a biologically
important enol; it is the highest energy
phosphorylated compound in living
systems
• Phosphoenolpyruvate is produced in the
next-to-last step in the metabolic pathway
called glycolysis, which is the first stage of
carbohydrate breakdown.

Keto-enol tautomers
Keto-enol tautomers
• In the final reaction of glycolysis the phosphoryl group from
phosphoenolpyruvate is transferred to adenosine diphosphate
(ADP).
• The reaction produces ATP, the major energy currency of the
cell
 Aldol
condensation

• The aldol condensation is a reaction in which aldehydes or

ketones react to form larger molecules.
• A new carbon-carbon bond is formed in the process
 • a very complex reaction that occurs in multiple steps.
• As shown in the equation below, the α-carbon (carbon-2)
of one aldehyde forms a bond with the carbonyl carbon
of a second aldehyde (shown in blue).
• A bond also forms between a hydrogen atom on that
same -carbon and the carbonyl oxygen (shown in red).

Aldol
Condensation
Aldol Condensation
• The result is similar when two ketones react
Aldol Condensation
• In the laboratory the aldol condensation is catalyzed by dilute base;
the same reaction occurs in our cells where it is catalyzed by an
enzyme.
• This reaction is one of many in a pathway that makes the sugar
glucose from smaller molecules; this pathway is called
gluconeogenesis (gluco- [sugar], neo- [new], genesis [to make]),
which simply means make new sugar.
• This pathway is critical during starvation or following strenuous
exercise where blood glucose concentrations may fall dangerously
low.
• Because the brain can use only glucose as an energy source, it is
essential that the body be able to produce it quickly
 Aldol
Condensation

• One of the steps in the pathway is an aldol condensation

between the ketone dihydroxyacetone phosphate and the
aldehyde glyceraldehyde-3-phosphate
• Dihydroxyacetonephosphate is a phosphorylated form of
dihydroxyacetone (DHA), the active ingredient in self-tanning
lotions
Aldol Condensation
• The speed and specificity of this reaction are ensured by the
enzyme aldolase.
• The product is the sugar fructose-1,6-bisphosphate, which is
converted by another enzyme into glucose-1,6-bisphosphate.
• Removal of the two phosphoryl groups results in a new
molecule of glucose for use by the body as an energy source.
Aldol Condensation
• Gluconeogenesis occurs under starvation conditions to provide
a supply of blood glucose to nourish the brain.
• However, when glucose is plentiful, it is broken down to provide
ATP energy for the cell.
• The pathway for glucose degradation is called glycolysis
where the reaction (Slide 75) is reversed.
• In general, aldol condensation reactions are reversible and are
called reverse aldols.