ALDEHYDES AND KETONES

Structures of Aldehydes and Ketones Compounds Containing a Carbonyl Group

- Both aldehydes and ketones contain a - Aldehydes: Carbonyl is attached to at
carbonyl (C=O) group. least one H atom in aldehydes
O O - Ketones: Carbonyl is directly attached
with two carbon atoms in ketones
C C - Carboxylic acids: carbonyl carbon atom
R H Ar H
bonded to a hydroxyl group.
aldehydes - Esters: carbonyl carbon atom bonded to
an oxygen atom
O O O - Amide: carbonyl carbon atom bonded to
a nitrogen atom
C C C O O
R R Ar R Ar Ar
C H C
ketones Aldehyde Ketone
- The general formula for the saturated Functional Group Functional Group
homologous series of aldehydes and O O O
ketones is: CnH2nO C O
C OH C NH
- In a linear expression, the aldehyde group is
Carboxylic Acid Ester Amide
often written as: CHO Functional Group Functional Group Functional Group

O
The Aldehyde and Ketone Functional Groups
C - Aldehyde functional group: –CHO
H3C H is equivalent to CH3CHO - Ketone functional group: carbonyl carbon
- In the linear expression of a ketone, the (C=O) attached to carbon atoms
carbonyl group is written as: CO - Cyclic aldehydes are not possible but cyclic
ketones are known
O - Cyclic ketones are not heterocyclic ring
systems
C
H3C CH3 is equivalent to CH3COCH3
Naming Aldehydes and Ketones
IUPAC Rules for Naming Aldehydes
The Carbonyl Group
1. To establish the parent’s name, select the
- Carbonyl group: A carbon atom double- longest continuous chain of carbon atoms
bonded to an oxygen atom that contains the aldehyde group.
- Aldehydes and ketones are the compounds 2. The carbons of the parent chain are
which contain a carbonyl functional group numbered starting with the aldehyde group.
- C=O bond is polar (oxygen gets partial Since the aldehyde group is at the
negative and carbon gets partial positive beginning (or end) of a chain, it is
charge) C=C is non polar understood to be number 1.
- All carbonyl groups have a trigonal planar 3. Form the parent aldehyde name by
structure
dropping the –e from the corresponding
- Compounds with C=O and C=C both exhibit
alkane name and adding the suffix –al.
different chemistry
4. Other groups attached to the parent chain
are named and numbered as we have done
before.
 ALDEHYDES AND KETONES

Naming Aldehydes 2. Form the parent’s name by dropping the –e

from the corresponding alkane name and
O add the suffix –one.
3. If the chain is longer than four carbons, it is
C
H3C H
numbered so that the carbonyl group has
ethanal the smallest number possible; this number
O
is prefixed to the parent’s name of the
ketone.
C 2 3 4 5 6 4. Other groups attached to the parent chain
H 1 CH2CH2CHCH2CH3
are named and numbered as we have done
CH3 before.
4-methyhexanal Naming Ketones
O O
IUPAC Names of Selected Aldehydes
C 1 C 3 4 5
H3C CH3 H3C 2 CH2CH2CH3
propanone 2-petanone

1 2 C 4 5 6 7 8
H3CH2C 3 CH2CH2CHCH2CH3

6-methyl-3-octanone CH3

Common Names for Ketones

O O

Common Names for Aldehydes C C

O O H3C CH3 H3C CH2CH3
propanone butanone
C C
H H H CH3 acetone methyl ethyl ketone, MEK
formaldehyde acetaldehyde

O Formaldehyde
- Simplest aldehyde and has one carbon
C
atom
H
- It is synthesized by oxidation of methanol
- Mainly used for the manufacturing of
polymers
benzaldehyde - Bubbling formaldehyde through water
produces formalin (formaldehyde in water
Dialdehydes with pungent smell)
- In dialdehydes, the suffix –dial is added to - Formalin is used for preserving biological
the corresponding hydrocarbon name. specimens
- In formalin formaldehyde is present in the
O O form of HO-CH2-OH

Acetone
HCCH2CH2CH
- Simplest ketone.
- Colorless liquid with mild sweet odor.
butanedial - Excellent solvent: it is miscible in both water
IUPAC Rules for Naming Ketones
and organic solvents.
1. To establish the parent’s name, select the - Acetone is the main ingredient in gasoline
longest continuous chain of carbon atoms treatments designed to solubilize water in
that contain the ketone group. the gas tank and allow it to pass through the
engine in miscible form.
 ALDEHYDES AND KETONES

- Major component of nail polish remover.

- Patients with diabetes produce large
amounts of acetone.
- Diabetic breath has mild sweet odor
because of acetone.
- Presence of acetone in urine indicates
diabetes.

Naturally Occurring Aldehydes and Ketones

- Aldehydes and ketones occur widely in
nature
- Such compounds have higher molecular
masses, pleasant odors and flavors
- Often used in consumer products such as
perfumes, air fresheners, etc.,). Physical Properties of Aldehydes and Ketones
- Example: Butanedione
- The unmistakable odor of melted butter is Physical State at Room Temperature
largely due to the four-carbon diketone - Aldehydes:
butanedione. - C1-C2 aldehydes are gases
- C3-C11 straight-chain aldehydes are liquids
Bonding and Physical Properties - >C11 aldehydes are solids
Bonding Ketones:
- The carbon atom of the carbonyl group is - Lower molar mass ketones are colorless
sp2-hybridized and is joined to three other liquids
atoms by sigma bonds.
- The fourth bond is made by overlapping p Boiling and Melting Points
electrons of carbon and oxygen to form a pi - Intermediate between alcohols and alkanes
bond between the carbon and oxygen - Higher boiling points than alkanes because
atoms. of dipole–dipole attractions between
- Bonding carbonyl groups in these molecules.
- Because the oxygen atom is considerably
more electronegative than carbon, the C=O O − +C
group is polar.
+
- Many of the chemical reactions of aldehydes
C − O
and ketones are due to this polarity.

Solubility
- Water molecules can hydrogen-bond with
aldehyde and ketone molecules, which
C O
-
causes low-molecular-mass aldehydes and

+ ketones to be water soluble.

- Aldehydes and ketones with longer
hydrocarbon chains are less soluble or
Properties insoluble in water.
- Unlike alcohols, aldehydes and ketones
cannot hydrogen-bond to themselves,
because no hydrogen atom is attached to
the oxygen atom of the carbonyl group.
- Aldehydes and ketones, therefore, have
lower boiling points than alcohols of
comparable molar mass.
 ALDEHYDES AND KETONES

Chemical Properties of Aldehydes and Ketones Biochemical Oxidation of Aldehydes

- When our cells ‘burn’ carbohydrates, they
Reactions of Aldehydes & Ketones take advantage of the aldehyde reactivity.
- Oxidation: aldehydes only - The aldehyde is oxidized to a carboxylic
- Reduction: aldehydes and ketones acid and is eventually converted to carbon
- Addition: aldehydes and ketones dioxide, which is then exhaled.
- This stepwise oxidation provides some of
Oxidation of Aldehydes the energy necessary to sustain life.
- Aldehydes are easily oxidized to carboxylic
acids by a variety of oxidizing agents, Reduction of Aldehydes & Ketones
including (under some conditions) oxygen of - Aldehydes and ketones are easily reduced
the air. to alcohols.
O O O
3 3 H2/Ni
RCH2OH
C + Cr2O72- + 8 H+ C + 3 Cr3+ + 4H2O C heat
R H primary
R H R OH alcohol
Tollens’ test
O
H2/Ni OH
- The Tollens test (silver-mirror test) for
C heat
aldehydes is based on the ability of silver
ions to oxidize aldehydes. R R RCHR
O O secondary
alcohol
C + 2 Ag+ NH3 C
+ 2 Ag (s)
Addition Reactions of Aldehydes & Ketones
H2O
R H R O-NH4+ Common addition reactions:
- Addition of alcohols: hemiacetal, hemiketal,
Fehling and Benedict Tests acetal, ketal
- Fehling and Benedict solutions contain Cu2+ - Addition of hydrogen cyanide (HCN):
ions in an alkaline medium. cyanohydrin
- In these tests, the aldehyde group is - Aldol Condensation (self-addition)
oxidized to an acid by Cu2+ ions.
O O Reaction of Aldehydes and Ketones with
Alcohols
- Aldehydes and ketones react with alcohols
C + 2 Cu+2 NaOH C + 2 Cu2O (s)
to form hemiacetals and acetals.
H2O
R H blue R O-Na+ brick red - Hemiacetal formation: A hemiacetal is an
organic compound in which a carbon atom
Tollens’, Fehling, and Benedict Tests is bonded to both a hydroxyl group (—OH)
- Because most ketones do not give a and an alkoxy group (—OR).
positive with Tollens, Fehling, or Benedict - A hemiacetal can also be formed due to the
solutions, these tests are used to distinguish reaction between an —OH and C=O
between aldehydes and ketones. functional groups with in the same
O molecule.
- Such a reaction produces a cyclic
C + 2 Cu+2 NaOH no reaction hemiacetal
R R
H2O - Cyclic hemiacetals are more stable

O Acetal Formation and Hydrolysis

- Acetal Formation: An acetal is an organic
NH3 compound in which a carbon atom is
C + 2 Ag+ no reaction
H2O bonded to two alkoxy groups (—OR).
R R
 ALDEHYDES AND KETONES

- Acetal Hydrolysis: Undergo hydrolysis in Aldol Condensation (Self-Addition)

acidic solution to form the aldehyde or - In a carbonyl compound, the carbon atoms
ketone and alcohols that originally reacted are labeled alpha (), beta (), gamma (),
to form the acetal. delta (), and so on, according to their
positions with respect to the carbonyl group.
Addition of Alcohols -C-C-C-C=O
- Aldehydes react with alcohols in the - The hydrogen atoms attached to the -
presence of a trace of acid to form carbon have the unique ability to be more
hemiacetals: easily released as protons than other
O OH hydrogens within the molecule.
H + - An aldehyde or ketone that contains -
+ CH3OH HC CH2CH3 hydrogens may add to itself or to another -
C
H CH2CH3 hydrogen containing aldehyde or ketone.
OCH3
propanal O
1-methoxy-1-propanol
(propionaldehyde methyl hemiacetal) C
- In the presence of excess alcohol and H CH3 O OH O
strong acid such as dry HCl, aldehydes or H H
dilute
hemiacetals react with a second molecule of C
NaOH CH C
the alcohol to give an acetal: H3C H2C H
H C H
OH OCH3
dry HCl aldol
H
HC CH2CH3 + CH3OH HC CH2CH3 +H2O (3-hydroxybutanal)

OCH3 OCH3 Common Aldehydes and Ketones

Formaldehyde (Methanal)
1,1-dimethoxypropane
- Formaldehyde is made from methanol by
(propionaldehyde dimethyl acetal)
reaction with oxygen (air) in the presence of
a silver or copper catalyst.
Addition of Alcohols to Aldehydes and Ketones
- 2 CH3OH + O2 → 2H2C=O + 2H2O
OH OH OR' OR' - Formaldehyde is widely used in the
synthesis of polymers.
C C C C
R R R R
H
OR' R
OR'
H
OR'
R
OR' Acetaldehyde (Ethanal)
hemiacetal hemiketal acetal ketal - Its principal use is as an intermediate in the
manufacture of other chemicals, such as
Addition of Hydrogen Cyanide acetic acid and 1-butanol.
- The addition of HCN to aldehydes and
Acetone and Methyl Ethyl Ketone
ketones forms a class of compounds known
- Acetone is used as a solvent in the
as cyanohydrins:
manufacture of drugs, chemicals, and
explosives. It is also used as a solvent.
- Methyl ethyl ketone (MEK) is also widely
used as a solvent, especially for lacquers.

Condensation Polymers
Phenol-Formaldehyde Polymers (Bakelite)
- Each formaldehyde molecule reacts with
two phenol molecules to eliminate water.
The polymer is then formed.
 ALDEHYDES AND KETONES

OH OH

O
+ +
C
H H

OH OH
H2
C
+ H2O

- Polymers of this type are still used,

especially in electrical equipment, because
of the insulating and fire-resistant
properties.
Formaldehyde-Based Polymers
- Formaldehyde is a prolific “polymer former”
- Under acidic conditions, reaction between
formaldehyde and phenol forms a phenol–
formaldehyde network polymer

Sulfur-Containing Carbonyl Groups

- Replacement of carbonyl oxygen with sulfur
produces thioaldehydes (thials) and
thioketones (thiones)
➢ These are unstable and readily
decompose.
- Replacement of the carbonyl carbon atom
with sulfur produces sulfoxides.
➢ Sulfoxides are much more stable than
thiocarbonyls
➢ Most important example: DMSO
(dimethyl sulfoxide)
➢ DMSO is an odorless liquid with
excellent solvent properties
➢ DMSO is quickly absorbed into the body
and is known to relieve pain and
inflammation
➢ Not approved by the FDA for medical
uses because of possible side effects