Organic Chemistry

Aldehyde and Ketones

Dr. Dikdik Kurnia

Kurnia,, M.Sc

Laboratorium Kimia Organik – Jurusan Kimia

Fakultas Matematikan dan Ilmu Pengetahuan Alam
Universitas Padjadjaran
2009
 Aldehyde and Ketones
1. What are the kinds of carbonyl groups, and how they differ?
Be able to recognize and draw the structures of the important
families of carbonyl compounds.
2. What are the general properties of aldehyde and ketones?
Be able to describe such properties as polarity, hydrogen bonding,
and water solubility.
3. How are ketones and aldehyde named?
Be able to name the simple members of these families and write
their structure, given the names.
4. What are some of the significant application and occurrences of
aldehydes and ketones?
Be able to identify major applications and occurrences of each
family of compounds and describe some important members of
each family.
5. What are the major chemical reactions of aldehyde and ketones?
Be able to describe and predict the products of the oxidation and
reduction of aldehyde and ketones, and their addition of alcohols.
 Aldehyde and Ketones
6. What are hemiacetals and acetals?
Be able to recognize hemiacetals and acetals, describe the
conditions under which they are formed, and predict the product
of acetal hydrolysis.
7. What is the adol reaction and why is it important in
biochemistry?
Be able to describe an aldol reaction, predict the products, and
explain why it is important in biochemitry.
 KINDS OF CARBONYL COMPOUNDS

Every carbonyl group contains a carbon-oxygen double bond in the same way that an
alkene grouping contain a carbon-carbon double bond.

The two most simple types of carbonyl compounds:

a. Aldehyde, in which the carbonyl group has one R and one H atom on the
carbonyl carbon atom.
b. Keton, in which there are two R groups on the carbonyl carbon
 KINDS OF CARBONYL COMPOUNDS

There are many different kinds of carbonyl compounds, depending on what other
substituents are bonded to the carbonyl-group carbon atom.

Aldehyde RCHO have a carbon substituent and a hydrogen bonded to

the carbonyl group

Ketone RCOR' have two carbon substituents

Carboxylic acids RCOOH have a carbon and a hydroxyl and a hydroxyl (—OH)

Anhydrides RCO2COR' Have a carbon and an oxygen bonded to another R-

C=O group

Ester RCOOR' have a carbon and an alkoxyl (—OR)

Amide RCONH2 have a carbon and a nitrogen group (—NH2), NHR, or

NR2)
KINDS OF CARBONYL COMPOUNDS
 KINDS OF CARBONYL COMPOUNDS

Since oxygen attracts electrons more strongly than carbon, carbonyl groups are
strongly polarized, with a partial positive charge on carbon and a partial negative
charge on oxgen

Another property common to all carbonyl group is planarity.

The carbonyl carbon is surrounded by three regions of electron density, and the
bond angles between the three substituents on carbon are 120 or close to it.
 KINDS OF CARBONYL COMPOUNDS
It’s useful to classify carbonyl compounds into two groups based on their chemical
properties.

I. Aldeyde and Ketones

The carbonyl-group in these compounds is bounded to atoms (H and C) that
don’t attract electrons strongly, the bonds to the carbonyl-group carbon of
aldehydes and ketones are not strongly polar.
The compounds behave similarly.
II. Carboxylic acids, Esters, and Amides.
The carbonyl-group carbon in these compounds is bounded to an atom (O or N)
that does attract electrons strongly, the bonds are strongly polar.
Carboxylic acids, esters, anhydrides, and amides behave similarly in many ways.
 NAMING ALDEHYDE AND KETONES
Aldehyde, a compound that has a carbonyl group bonded to one carbon atoms and
one hydrogen atom, RCH=O.
Aldehyde are named systematically by replacing the final –e of the corresponding
alkane name with –al.
When Substituents are present, the chain is numbered beginning at the —CHO end.

Ketone, a compound that has a carbonyl group bonded to two carbon atoms, R2C=O.
Ketones are named systematically by replacing the final –e of the corresponding
alkane name with –one (pronounced “own”).
The numbering of the chain begins at the end nearer the carbonyl group.
 PROPERTIES OF ALDEHYDE AND KETONES
The polarity of the carbonyl group make aldehydes and ketones moderately polar
compounds.
They are higher boiling than alkanes with similar molecular weight.
Because they have no hydrogen atoms bonded to oxygen or nitrogen, however, their
molecules don’t hydrogen-bond with each other, and this makes aldehydes and
ketones lower boiling than alcohols.
In a series of compounds with similar molecular weights, the alkane is lowest boiling,
the alcohol is highest boiling, and the aldehyde and ketone fall in between.
 PROPERTIES OF ALDEHYDE AND KETONES
Aldehydes and ketones are soluble in common organic solvent, and those with fewer
than five carbon atoms are also solble in water because they’re able to hydrogen-
bond with water molecules

These simple aldehydes and ketones are exellent solvents because they dissolve both
polar and nonpolar compounds.
With increasing numbers of carbon atoms, aldehydes and ketones become more
alkane-like and less water-soluble.
PROPERTIES OF ALDEHYDE AND KETONES
 PROPERTIES OF ALDEHYDE AND KETONES

 No hydrogen bonding between aldehyde or ketone molecules, but they are polar
and lower boiling than alcohols, but higher boiling than alkanes.
 Common aldehydes and ketones are liquids (except gaseous formaldehyde).
 Simple aldehydes and ketones are water-soluble due to hydrogen bonding with
water molecules.
 Volatile aldehyde and ketones are flammable.
 Many have distinctive odors.
 Simple ketones are less toxic than simple aldehyde.
 SOME COMMON ALDEHYDE AND KETONES
Ketones are used in industry primary as solvent, and aldehydes are valuable as
reactants in organic synthesis and polymer formation.
In living things, aldehyde and ketone functional groups are present in a great many
compounds
 SOME COMMON ALDEHYDE AND KETONES
Formaldehyde, acetaldehyde and acetone are two simplest aldehydes and acetone,
the simplest
SOME COMMON ALDEHYDE AND KETONES
Formaldehyde (HCHO):
 At room temp. is a colourless gas with a pungent, suffocating odor.
 Highly toxic by ingestion, causing serious kidney damage, coma, and
death.
 Some aldehydes are good desinfectants, including the four-carbon
dialdehyde succinaldehyde (OHCCH2CH2CHO), a chemical sterilant used
for delicate surgical nstruments that can’t be sterilized by heat.
 In the chemical industry, the major use of formaldehyde is in polymers
with applications such as adhesives for binding plywood, foam insulation
used in houses, textile finished, and hard and durable manufactured
objects such as tetelphone parts.
SOME COMMON ALDEHYDE AND KETONES

Acetaldehyde (CH3CHO):
 A sweet-smelling, flammable liquid present in ripe fruits.
 It is less toxic than formaldehyde, and small amounts are produced in the
normal breakdown of carbohydrates.
 It’s a general narcotic, and large doses can cause respiratory failure.

Acetone (CH3COCH3):
 At room temp. is a liquid, the most widely used of all organic solvents.
 Highly volatile and is a serious fire and explosion risk when allowed to
evaporate in a closed space.
 OXIDATION OF ALDEHYDE
Oxidation, in organic chemistry, the removal of hydrogen from a molecule or
addition of oxygen to a molecule.

Reaction with a mild oxidizing agent that doesn’t affect other functional groups in a
molecule can be used as a test for the presence of an aldehyde group.
Tollens’ reagent, a dilute solution of silver nitrate in aqueous ammonia, rapidly yields
the ammonium salt of the carboxylic acid and silver metal as by-product.
Addition of an acid such as HCl then yields the carboxylic acid.
 OXIDATION OF ALDEHYDE
Tollens’ reagent, a dilute solution of silver nitrate in aqueous ammonia, rapidly yields
the ammonium salt of the carboxylic acid and silver metal as by-product.
Addition of an acid such as HCl then yields the carboxylic acid.
 OXIDATION OF ALDEHYDE

Benedict’s reagent, a reagent (Cu2+ in basic solution) that converts an aldehyde into a
carboxylic acid and yields a brick-red precipitate of Cu2O.
 REDUCTION OF ALDEHYDE AND KETONES
Reduction, in organic chemistry, the addition of hydrogen to a molecule or the
removal of oxygen from a molecule.

The reduction of aldehydes and ketones is usually accomplished by treatment with

sodium borohydride, NaBH4.
When mixed with a ketone or aldehyde, NaBH4 transfer one of its hydrogens as
hydride ion (:H-).
The hydride ion contributes both electrons to a covalent bond to the carbonyl carbon,
forming an anion.
Aqueous acid is the added, H+ adds to the oxygen, and a neutral alcohol product
results.
 REDUCTION OF ALDEHYDE AND KETONES
Aldehydes are converted into primary alcohols (RCHO RCH2OH).

Ketones are converted into secondary alcohols (R2CO R2COH)

 REDUCTION OF ALDEHYDE AND KETONES

The reduction of aldehydes and ketones takes two steps, addition of :H- and addition
of H+ polarity of the carbonyl group.

Living organism use nicotinamide adenine dinucleotide (NADH) as a biological source

of hydride ion (:H-).
REACTION WITH ALCOHOL: HEMIACETAL AND ACETALS

Addition reaction of aldehyde and ketones

Addition of an alcohol or other reagent to the carbon-oxygen double bond to give a
carbon-oxygen single bond.
Hemiacetal
A compound that has both an alcohol-like —OH group and an ether-like —OR group
bonded to the same carbon atom.

Hemiacetal Formation
Aldehydes and ketones undergo addition reactions with alcohol.
The C=O bond is converted to a single C—O bond.
The H from the alcohol bonds to the carbonyl-group oxygen, and the OR from the
alcohol bonds to the carbonyl-group carbon.
REACTION WITH ALCOHOL: HEMIACETAL AND ACETALS
Two important feature of reaction,
The negatively polarized alcohol oxygen atom that adds to the positively polarized
carbonyl carbon, just as negatively charged hydride ion adds to the positively
polarized carbonyl oxygen during reduction.
Hemiacetals rapidly revert back to aldehydes or ketones by loss of alcohols.
Hemiacetal compounds are often too unstable to be isolated.
REACTION WITH ALCOHOL: HEMIACETAL AND ACETALS

The one major exception to this rule occurs in the case of sugar such as glucose in
which the OH and CHO functional groups that react are part of same molecules.
The resulting cyclic hemiacetal is more stable than a noncyclic hemiacetal.
REACTION WITH ALCOHOL: HEMIACETAL AND ACETALS
Acetal
A compound that has two ether-like —OR group bonded to the same carbon atom.

Acetal Formation
If a small amount of acid catalyst is added to the reaction of an alcohol and a
carbonyl compound, the initially formed hemiacetal is converted into an acetal.
Acetals are quite stable and are easily isolated.
The H from the alcohol bonds to the carbonyl-group oxygen, and the OR from the
alcohol bonds to the carbonyl-group carbon.
REACTION WITH ALCOHOL: HEMIACETAL AND ACETALS

Acetal Formation
If a small amount of acid catalyst is added to the reaction of an alcohol and a
carbonyl compound, the initially formed hemiacetal is converted into an acetal.
Acetals are quite stable and are easily isolated.
The H from the alcohol bonds to the carbonyl-group oxygen, and the OR from the
alcohol bonds to the carbonyl-group carbon.
REACTION WITH ALCOHOL: HEMIACETAL AND ACETALS

Acetal Formation
If a small amount of acid catalyst is added to the reaction of an alcohol and a
carbonyl compound, the initially formed hemiacetal is converted into an acetal.
Acetals are quite stable and are easily isolated.
The H from the alcohol bonds to the carbonyl-group oxygen, and the OR from the
alcohol bonds to the carbonyl-group carbon.
REACTION WITH ALCOHOL: HEMIACETAL AND ACETALS

Hydrolysis
The breakdown of a compound, such as an acetal, by reaction with water; the H’s
and O of water add to the atoms of the broken bonds.
Acetal Hydrolysis
Acetals react with aqueous acid to regenerate the original keton and aldehyde plus
two molecules of alcohol.
 ALDOL REACTION OF ALDEHYDE AND KETONES
Aldol Reaction
The reaction of a ketone or aldehyde to form a hydroxy ketone product on treatment
with a base catalyst.
In the reaction,
 a bond forms between the carbon atom next to the carbonyl group of one molecul
and the carbonyl-group carbon of the second molecules.
 The product formed by joining together two molecules of starting material, is a
hydroxy ketone or a hydroxy aldehyde.
 ALDOL REACTION OF ALDEHYDE AND KETONES
Limitation of Aldol Reactions:
The aldehyde or ketone starting material must have a hydrogen atom on the carbon
next to the carbonyl group.
If there is no such hydrogen present, an aldol reaction can’t take place.