ORGANIC

CHEMISTRY
CHM557
CHAPTER 1:
ALDEHYDES AND
KETONES I:
OXIDATION, REDUCTION
AND SYNTHESIS
 COURSE
LESSON PLAN
At the end of the chapter, student
should be able to understand
▪ Introduction to carbonyl compounds
▪ Nomenclature of aldehydes and
ketones
▪ Physical properties of aldehydes and
ketones
▪ Reduction of aldehydes and ketones
▪ Synthesis of aldehydes and ketones
▪ Tests for aldehydes and ketones
INTRODUCTION TO
CARBONYL
COMPOUNDS
 The Carbonyl Group
⧫ The carbonyl group consists of
● one s bond formed by the overlap of sp2 hybrid orbitals,
and
● one p bond formed by the overlap of parallel 2p orbitals
Carbonyl Compounds
 Structure of Aldehydes
⧫ The functional group of an aldehyde is a carbonyl
group bonded to a H atom
● in methanal, it is bonded to two H atoms
● in all other aldehydes it is bonded to one H and one
carbon atom
 Structure of Ketones

⧫ The functional group of a ketone is a carbonyl group

bonded to two carbon atoms
NOMENCLATURE OF
ALDEHYDES AND
KETONES
 Naming
Aldehydes
 IUPAC NAMES OF ALDEHYDES

The IUPAC names of aldehydes are obtained by

dropping the –e and adding -al to the name of
the parent hydrocarbon.

butane al
butanal
The parent hydrocarbon is the longest
chain that carries the –CHO group.

This chain has 4

carbon atoms

3 2

1
4
The parent hydrocarbon is the longest chain
that carries the –CHO group.

This chain has 5

carbon atoms

5 4 3 2

1
The –CHO group is always at the beginning of
the carbon chain. The carbonyl carbon is
numbered as carbon 1.

5 4 3 2

3-methylpentanal
 For unsaturated aldehydes, show the
presence of the C=C by changing the infix
-an- to -en-
 COMMON NAMES OF ALDEHYDES

● The common names of aldehydes are derived from the

common names of the carboxylic acids.
● The –ic acid or –oic acid ending of the acid name is
dropped and is replaced with the suffix –aldehyde.

butyric acid butyraldehyde

 NOMENCLATURE OF CYCLIC ALDEHYDES
⧫ Aliphatic aldehydes containing a ring as well as aromatic
aldehydes in which the aldehyde (-CHO) group is attached
directly to the benzene ring are named by adding suffix
carbaldehyde to the name of the corresponding hydrocarbon.

2-cyclopentenecarbaldehyde
 NOMENCLATURE OF AROMATIC COMPOUNDS

If the aldehyde group is not attached directly to the benzene ring,

the aldehyde is named as an aryl derivatives of the corresponding
aldehyde.
 Naming
Ketones
 IUPAC NAME OF KETONES
▪ The IUPAC name of a ketone is derived from the
name of the alkane corresponding to the longest
carbon chain that contains the ketone-carbonyl
group.
▪ The parent name is formed by changing the –e
ending of the alkane to -one.

propane propanone
one
 If the carbon chain is longer than 4 carbons, the chain is
numbered. Numbering is begin from the carbon which
closest to the C=O so that the carbonyl carbon has the
smallest number possible, and this number is prefixed to
the name of the ketone.

This end of the chain is closest to the C=O.

Begin numbering here.
1 2 3 4 5 6

IUPAC name: 3-hexanone

New IUPAC name: hexan-3-one
Examples:
 COMMON NAME OF KETONES
The common names of ketones are derived by naming
the alkyl or aryl groups attached to the carbonyl
carbon followed by the word ketone.

ethyl propyl

ethyl propyl ketone

IUPAC nomenclature and common names for aldehyde
and ketone compounds

Compound Structure formula IUPAC Common name

nomenclature
Aldehyde H2C=O Methanal Formaldehyde

CH3CH=O Ethanal Acetaldehyde

CH3CH2CH=O Propanal Propionaldehyde

CH3CH2CH2CH=O Butanal Butyraldehyde

Ketone CH3COCH3 Propanone Acetone

CH3CH2COCH3 2-Butanone Ethyl methyl ketone

CH3CH2CH2COCH3 2-Pentanone Methyl propyl ketone

CH3CH2COCH2CH3 3-Pentanone Diethyl ketone

 NOMENCLATURE OF CYCLIC KETONES AND AROMATIC
COMPOUNDS

✔ The parent name is formed by changing the –e ending of the

cycloalkane to -one.
✔ Carbonyl carbon is designated C1.

✔ Aromatic compound:
- phenyl is used as part of the name.
 NAME AS SUBSTITUENT
A ketone or aldehyde group can also be named as a substituent on a molecule
with a higher priority functional group.

MAIN GROUPS

Acids
Esters
Aldehydes
Ketones
decreasing Alcohols
priority Amines
Alkenes
Alkynes
Alkanes
Ethers
Halides
 NAME AS SUBSTITUENT
o The ketone carbonyl is designated by the prefix oxo-.
o The –CHO group is named as a formyl group.
o Aldehyde priority is higher than ketone.
 Exercise 1
Give IUPAC names for the following compounds

a. b.

d.
c.
 PHYSICAL
PROPERTIES OF
ALDEHYDES AND
KETONES
Oxygen is more electronegative than carbon (3.5 vs 2.5)
and, therefore, a C=O group is polar
-aldehydes and ketones are polar compounds and interact in
the pure state by dipole-dipole interaction
-they have higher boiling points and are more soluble in
water than nonpolar compounds of comparable molecular
weight
 PHYSICAL PROPERTIES OF ALDEHYDES AND KETONES
1. BOILING POINTS
✔Boiling points for ketones and aldehydes are higher than
hydrocarbons and ethers of similar molecular weights.
- Reason: Polarization of the carbonyl group creates dipole-
dipole attractions between the molecules of ketones and aldehydes.
This attractions resulting in higher boiling points for ketones and
aldehydes.

✔Boiling points of ketones and aldehydes are lower than alcohols of

similar molecular weight.
- Reason: Ketone and aldehyde did not have O-H and N-H bonds.
Thus, these compounds can not form hydrogen bonds with each
other. They rely only on intermolecular dipole-dipole interactions.
Boiling points of alkane, ether, aldehyde, ketone and
alcohol of similar molecular weight
2. WATER SOLUBILITIES
o Ketones and aldehydes have lone pairs of electrons and can act
as hydrogen bond acceptors with other compounds having O-H
or N-H bonds.
o For example, the –OH hydrogen of water or an alcohol can
form a hydrogen bond with unshared electrons on a carbonyl
oxygen atom.

δ+ δ-
δ+ δ-
δ+ δ+
δ+ δ+

hydrogen bonding δ-
hydrogen bonding δ-
o Because of the hydrogen bonding, ketones and aldehydes are
good solvents for polar hydroxylic substances such as alcohols.

o Ketones and aldehydes are soluble in water.

- ketones and aldehydes having ≤ 5 carbons are H2O soluble
because they can hydrogen bond with H2O.

- ketones and aldehydes having more than 4 carbon are H2O

insoluble because the nonpolar alkyl portion is too large to
dissolve in the polar H2O solvent.

- the solubility of ketones and aldehydes in water decreases

with the increasing length of the carbon chain.
 REDUCTION OF
ALDEHYDES AND
KETONES
 Reduction of Aldehydes and Ketones

Deoxygenation of aldehydes
Reduction to alcohol and ketones

Aldehydes reduced to 1° alcohols C=O group reduced

Ketones reduced to 2° alcohols to a -CH2- group

Reagents: Methods:
Catalytic hydrogenation Clemmensen reduction
Metal Hydride Reduction Wolff–Kishner reduction
Reduction of Aldehydes and Ketones
Reduction to alcohol

Deoxygenation of aldehydes and ketones

 REDUCTION
TO ALCOHOL
Reducing a ketone or an aldehyde to an alcohol
involves adding 2 hydrogen atoms across the C=O
 1. CATALYTIC HYDROGENATION
a. Hydrogenation with Raney nickel catalyst
Raney nickel is finely divided Ni powder saturated with hydrogen gas.
Uses:
- Reduction of ketone to secondary alcohol
- Reduction of aldehyde to primary alcohol
- Reduction of alkenes to alkanes
It will attack the alkene first, then the carbonyl.
Examples:
b. Hydrogenation with catalyst palladium on carbon, or Pd/C

▪ Uses:
1. Reduction of alkenes to alkanes
2. Reduction of ketone to secondary alcohol
3. Reduction of aldehyde to primary alcohol

Reduction of ketone to
secondary alcohol

Reduction of aldehyde to
primary alcohol
✔ Alkenes are much more reactive toward catalytic hydrogenation than
most other unsaturated functional groups such as aldehydes, ketones,
and nitriles and the reaction is therefore quite selective.

✔ Example: C=C is reduced faster than a C=O, -CN, benzene with H2 (Pd/C).

C=O ketone DOES

NOT REDUCED

C=C is hydrogenated BUT C=O

ketone DOES NOT REDUCED when
1 equivalent of H2 is used
 When a compound contains both a carbonyl group and a
carbon–carbon double bond reacts with excess H2 gas in Pd/C,
both functional groups are reduced.
COMPARISON BETWEEN CATALYTIC HYDROGENATION USING
DIFFERENT HETEROGENEOUS CATALYSIS

H2 in the presence of Raney Ni

reduces BOTH π bonds (C=C and
C=O)

ONE EQUIVALENT OF H2 reduces

the C=C selectively. C=O KETONE
DOES NOT REDUCED.

Excess H2 reduces BOTH π bonds

(C=C and C=O)
 2. METAL HYDRIDE REDUCTION

o The most common laboratory reagents for the reduction of

aldehydes and ketones are NaBH4 and LiAlH4.
o Both reagents are sources of hydride ion, H:-, a very powerful
nucleophile.
 2a. Sodium Borohydride (NaBH4)

▪ NaBH4 is not sensitive to moisture and a source of hydrides

(H-).

▪ The reactions takes place in alcohols, ethers and water.

▪ ONLY REACTS with carbonyl of aldehyde or ketone or acid

chloride, NOT with carbonyls of esters or carboxylic acids.

▪ DO NOT reduce carbon-carbon double bonds.

▪ It adds the equivalent of “ H- ”

2a. Sodium Borohydride (NaBH4)
 Mechanism of hydride reduction of a carbonyl group
✔ The mechanism involves:

i. Addition of nucleophilic hydride ion, H-, to the positively

polarized electrophilic carbon of C=O to form an alkoxide ion
intermediate
ii. Protonation of the alkoxide ion intermediate
 Mechanism of NaBH4 Reduction
⧫ The key step in metal hydride reduction is transfer of a hydride ion to
the C=O group to form a tetrahedral carbonyl addition compound
(alkoxide ion).
⧫ Protonation of the intermediate with dilute acid to form alcohols.

1. Hydride attacks the carbonyl carbon, forming an alkoxide ion

Alkoxide ion
2. Protonation by dilute acid to form alcohol
 2b. Lithium Aluminium Hydride(LiAlH4 or LAH)

▪ LiAlH4 is source of hydrides (H-)

▪ Stronger reducing agent than NaBH4, but dangerous to work
with.
▪ Uses:
- Reduces ketones and aldehydes into the corresponding
alcohol.
- Reduces esters and carboxylic acids to 1o alcohols.
▪ LiAlH4 has NO EFFECT on the benzene ring or the double bond.
▪ Like NaBH4, it adds the equivalent of “ H- ”.
▪ Unlike NaBH4, LiAlH4 reacts violently with water, methanol,
and other protic solvents. Reductions using it are carried out in
diethyl ether or tetrahydrofuran (THF).
Examples
Mechanism of Reduction of Aldehyde and/or
Ketone with NaBH4 and LiAlH4

https://www.youtube.com/watch?v=uWJRx-5n1yw
Comparison of Reducing Agents

❑ LiAlH4 is stronger.
❑ LiAlH4 reduces more
stable compounds
which are resistant to
reduction.
NaBH4 is more selective
Only C=O ketone reduce.
C=O carboxylic acid does
not reduced

Both C=O reduce

 COMPARISON BETWEEN CATALYTIC REDUCTION AND
METAL HYDRIDE REDUCTION
⧫ Metal hydride reducing agents DO NOT normally reduce
carbon-carbon double bonds.

1. NaBH4
2. H3O+

1. LiAlH4, ether
C=C does not C=C reduce
2. H3O+
reduced to –CH2-

C=C does not reduced

 REDUCTION REACTIONS
Groups H2, Raney Ni H2, Pd/C i. NaBH 4, alcohol i. LiAlH 4, ether or
ii. H 3O+ THF
ii. H 3O+ or H 2O
Alkene Alkane Alkane No reaction No reaction

Aldehyde (C=O) 1º alcohol 1º alcohol 1º alcohol 1º alcohol

Ketone (C=O) 2º alcohol 2º alcohol 2º alcohol 2º alcohol

Carboxylic acid No reaction No reaction No reaction 1º alcohol

Ester No reaction No reaction No reaction 1º alcohol

Amide No reaction No reaction No reaction Amine

Acid chloride - - 1º alcohol 1º alcohol

Nitrile (-CN) Primary amine Primary amine No reaction Primary amine

Note: (For compound that contain C=C

and other functional groups)
• Alkene is reduced more faster with H2,
Pd/C than C=O, -CN and benzene. If1
equivalent H2, Pd/C is used, ONLY
alkene is hydrogenated.
• Excess H2, Pd/C: Alkene along with
C=O or -CN are reduced.
 Exercise 2
Determine the structure of products or reagents or starting
compounds that would complete the following reactions.

a.

b.

c.

d.
 Exercise 2 (Continued)

e.
DEOXYGENATIO
N OF
ALDEHYDES AND
KETONES
 REMOVAL OF CARBONYL GROUP :
DEOXYGENATION
❖ Deoxygenation: Replacement of the C=O of a
ketone or aldehyde with two hydrogen atoms.
⇒ C=O to -CH2-

❖ Two methods:
i. Clemmensen reduction if molecule is stable in hot
acid.
ii. Wolff-Kishner reduction if molecule is stable in
very strong base.
 i. Clemmensen Reduction
Refluxing an aldehydes or ketones with amalgamated zinc (zinc treated
with mercury salts) in aqueous HCl converts the carbonyl group to a
methylene group.

Examples:
• The substrate must be unreactive to the strongly acidic conditions
of the Clemmensen reduction. Acid-sensitive substrates should be
reacted in the Wolff-Kishner reduction, which utilizes strongly
basic conditions.

• Substituents (examples, hydroxyl, alkoxyl & halogens) at alpha

position of the carbonyl group are labile. The substituents are
reduced first followed by the reduction of the resulting
unsubstituted aldehyde or ketone to the parent hydrocarbon.

• Clemmensen reduction might give a dehydration by-products by

the acid catalyzed reaction.
 ii. Wolff-Kishner Reduction
o The aldehyde or ketone and hydrazine are refluxed with
KOH or potassium tert-butoxide in a high-boiling solvent.

o High-boiling solvent: ethylene glycol, diethylene glycol, or

DMSO.

o A molecule of nitrogen is lost in the last steps of the reaction.

ii. Wolff-Kishner Reduction

or
Mechanism of
Wolff-Kishner
Reduction

https://www.youtube.com/watch?v=u0j-ireI0W8
 Exercise 3
Provide the products/reagent for the following reactions.

1.

2.

3.

4.
SYNTHESIS OF ALDEHYDES
AND KETONES
Synthesis of aldehydes
1. Reduction of acid chlorides and esters
2. Oxidation:
i. Oxidation of primary alcohols
ii. Oxidation cleavage of alkenes by
ozonolysis

Synthesis of ketones
1. Oxidation of secondary alcohols
2. Oxidation cleavage of alkenes by
ozonolysis
SYNTHESIS OF
ALDEHYDES
 1. REDUCTION OF ACID CHLORIDES AND
ESTERS
❖ Reduction to an aldehyde can be accomplished by using a more
reactive carboxylic acid derivatives (examples, acid chloride, ester)
or nitrile and a less reactive hydride source.

❖ Cannot used LiAlH4 because

LiAlH4 is a strong reducing agent that reduces acids, acid
chlorides, anhydrides and esters to primary alcohols.

❖ Therefore, a sterically hindered and less reactive aluminum hydride

reagent such as diisobutylaluminum hydride (DIBAL-H or DIBAH) or
lithium tri-tert-butoxyaluminum hydride (LiAl-+H(O-t-Bu)3) is used to
reduce acid chloride and ester to aldehyde.
 a. REDUCTION OF ESTERS TO
ALDEHYDES
• Esters can be converted to aldehydes using
diisobutylaluminum hydride (DIBAL-H or DIBAH).

• The reaction is usually carried out at -78oC to prevent

reaction with the aldehyde product.
 Diisobutylaluminium hydride (DIBAL-H)

A bulky “electrophilic” reducing agent which has two bulky isobutyl

groups which makes this reagent less reactive than LiAlH4.
Coordinates to its carbonyl host before delivering its hydride.
It reacts only once with the carbonyl carbon forming a stable
tetrahedral complex which will only fall apart during the workup
procedure. Thus, the carbonyl group will not reduce further to
alcohol.
Mechanism reduction of aldehyde from ester using DIBAL-H

1
Examples:
 b. REDUCTION OF ACID
CHLORIDES TO
ALDEHYDES
Lithium tri-tert-butoxyaluminum
hydride (LiAl-+H(O-t-Bu)3) and Rosenmund
diisobutylaluminium hydride reduction
(DIBAL-H or DIBAH).
i. Lithium tri-tert-butoxyaluminum hydride

LiAl-+H(O-t-Bu)3 is a
weaker reducing agent
than LiAlH4
 Reduction of acid chloride

Dry ice (solid CO2) Only 1 equivalent of very cold DIBAL-H is used to
sublimes at –78°C avoid further reduction of the aldehyde to an alcohol
 ii. ROSENMUND REDUCTION (CATALYTIC
HYDROGENATION)

Chemical reaction that reduces an acid chloride to

an aldehyde using hydrogen gas over palladium on
carbon poisoned with barium sulfate.
 2. OXIDATION
1. Oxidation of primary alcohol to aldehydes.

Can use any of these reagents:

a. Pyridinium chlorochromate (PCC) in CH2Cl2.

b. Chromium Based Reagents:

i. Sarett reagent: Complex of CrO3 • 2 Py which formed from
the addition of chromium trioxide to an excess of pyridine

ii. Collins reagent: Complex of chromium(VI) oxide with

pyridine (CrO3 • 2 Py complex) diluted in dichloromethane.
2. OXIDATION
Examples:
 PCC Reagents

▪ PCC is made from chromium trioxide under acidic conditions.

▪ It is used in organic solvents such as methylene chloride
(CH2Cl2).
▪ PCC will not fully oxidize a primary alcohol to the carboxylic
acid as does the Jones reagent.
▪ A disadvantage to using PCC is its toxicity.
2. Oxidation cleavage of alkenes by ozonolysis

❑ Ozonolysis:
- The reaction of alkenes with ozone (O3) to form an ozonide,
followed by hydrolysis of the ozonide to produce aldehydes
and /or ketone.
- Widely used to determine the position of the carbon-carbon
double bond.
- Ozonolysis is milder and both ketone and aldehydes can be
recovered without further oxidation.

H+ = acetic acid
 Examples:

* (CH3)2S can be replaced with H2O and Zn/H+

 Exercise 4
Provide the products/reagent for the following reactions. Include
intermediate(s) where necessary.

1.

2.

3.
SYNTHESIS OF
KETONES
 1. Oxidation of secondary
o
alcohols
2° alcohol becomes a ketone.
o Reagents:
a. Chromic acid reagent (H2CrO4) or Jones reagent
Preparation:
- Na2Cr2O7 or K2Cr2O7 is dissolved in aqueous acid such as dilute
H2SO4 or
- Chromium trioxide (CrO3) is dissolved in dilute H2SO4

b. Hot acidified KMnO4 (KMnO4/H2SO4)

c. Pyridinium chlorochromate (PCC) in CH2Cl2

d. Chromium based reagents:

i. Sarett reagent
ii. Collins reagent
Examples:
2. Oxidation cleavage of alkenes by ozonolysis
Same as aldehydes

H+ = acetic acid
TESTS FOR ALDEHYDES
AND KETONES

✔ TOLLENS’ TEST
✔ IODOFORM TEST
 TOLLEN’S TEST OR SILVER MIRROR TEST
FOR ALDEHYDES AND KETONES

❑ Test for identifying aldehydes. Simple hydrocarbons, ethers, ketones

and alcohols DO NOT REACT with Tollens’ reagent.

❑ Tollens’ reagent ([Ag(NH3)2]+) or called as ‘ammoniacal silver nitrate’

solution is a mixture of aqueous silver nitrate and ammonia.

❑ Contains the silver amine complex ion, [Ag(NH3)2]+

❑ Tollens’ reagent is a mild oxidising agent.

❑ Silver ion, Ag+ oxidized aldehyde to carboxylate ion.

❑ Silver ion is reduced to metallic silver in the form of a black suspension

or a silver mirror deposited on the wall of the test tube.
Complete equation:
 Example

silver mirror
 IODOFORM TEST
o Iodoform test use a solution of I2 in an alkaline medium such as NaOH
or KOH (oxidising agent).

o Iodoform test is useful for the methyl ketone group (CH3C=O) in

ethanal and methyl ketones.
o If an alkaline solution of iodine is warmed with an organic compound
and a bright yellow solid of triiodomethane (iodoform) is produced.
General synthetic outline or equation for iodoform test:

Example:
 IODOFORM TEST
o When ethanal warmed with this solution, triiodoethanal will be
formed as the intermediate product.

o Triiodoethanal then reacts with the base to form a bright yellow

solid (triiodomethane or iodoform).

Synthetic outline or Equation:

CH3CHO + 3I2 3NaOH CI3CHO

triidoethanal

Cl3CHO + NaOH HCOO- Na+ + CHI3 (s)

triiodomethane (iodoform)
o Iodoform test can be used to distinguish:
i) ethanal from other aldehydes, because ethanal is the only aldehydes
that gives a positive iodoform test.
ii) methyl ketones (ketones that contain CH3CO- group) give positive
iodoform test.

For example, propanone and phenylethanone give a bright yellow solid

(positive iodoform test), but 3-pentanone and diphenylmethanone which
does not contain methyl ketone group give negative iodoform tests (yellow
solution).

99
 SUMMARY OF TESTS FOR
ALDEHYDES AND KETONES

Test Reagent Observation

Tollens’ [Ag(NH3)2]+ Aldehyde: Formation of silver mirror.
Test Ketone: Silver mirror does not formed.
Iodoform I2/NaOH Positive test: Formation of bright yellow
Test solid (iodoform). Compounds which
have methyl ketone structure will give
positive test.
 Exercise 5
Provide the products/reagent for the following reactions. Include
intermediate(s) where necessary.

1.

2.

3.

4.
 Exercise 6
Consider the following schematic diagram

1. Provide suitable reagents for the conversion of compound P to

hydroxyester and from hydroxyester to compound Q.

2. Explain why LiAlH4 could not be used in the conversion of P to Q.

 Exercise 7

Reacting ethanol with PCC gives compound X which would also

give a positive result with iodoform test. Explain how
compound X gives a positive iodoform reaction. You may
include a synthetic outline to support your reasoning.
 Exercise 8
1. Compound A with a molecular formula of C5H10O gives a negative
result against iodoform test as well as Tollens’ test and shows a
strong absorption at 1715 cm-1 in its IR spectrum.

a. Suggest the possible structure of A.

b. Identify how many sets of signals can be found in the 1H NMR and
13
C NMR spectra of A.

c. Sketch a predicted 1H NMR spectrum of compound A by showing

all proton signals with estimated chemical shifts and multiplicity.