CHEM 254

ORGANIC REACTION MECHANISMS

CARBONYL COMPOUNDS
By

DR. (MRS) MERCY BADU

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Common Classes of Carbonyl Compounds

Class General Formula Class General Formula

O O
Ketones Aldehydes
R R' C
R H

O O
Carboxylic acids R OH Acid Chlorides R
C
Cl

O O

Esters R
C
O
R'
Amides R
C
NH2

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 CARBONYL COMPOUNDS - BONDING

Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar
the unhybridised 2p orbital of carbon is at 90° to these
it overlaps with a 2p orbital of oxygen to form a pi () bond

P ORBITAL

ORBITAL
PLANAR OVERLAP
WITH NEW
BOND ORBITAL
ANGLES
OF 120°

as oxygen is more electronegative than carbon the bond is polar

The Carbonyl Group (In Summary)

C O The carbonyl group

o The carbon–oxygen double bond consists of a sigma bond and a pi bond.

o The carbon atom is sp2-hybridized.
o The three atoms attached to the carbonyl carbon lie in a plane with bond angles of 120°.
o The pi bond is formed by overlap of a p orbital on carbon with an oxygen p orbital.
o There are also two unshared electron pairs on the oxygen atom.
o The C=O bond distance is 1.24A, shorter than the C-O distance in alcohols and ethers (1.43A).

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The carbonyl group ( In Summary)

• The local geometry around the carbonyl group is trigonal planar.

The rest of the molecule doesn’t have to be planar:

Local trigonal
planar geometry

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The Carbonyl Group (Properties)
o Oxygen is much more electronegative than carbon. Therefore, the electrons in the C=O bond are
attracted to the oxygen, producing a highly polarized bond.

o As a consequence of this polarization, most carbonyl reactions involve nucleophilic attack at the
carbonyl carbon, often accompanied by addition of a proton to the oxygen (electron rich).

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Structure of Aldehydes and Ketones
o Aldehydes and ketones are characterized by the presence of the carbonyl group.

o Aldehydes have at least one hydrogen atom attached to the carbonyl carbon atom.
The remaining group may be another hydrogen atom or any aliphatic or aromatic organic group.
The -CH=O group characteristic of aldehydes is often called a formyl group.
o In ketones, the carbonyl carbon atom is connected to two other carbon atoms.

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 CARBONYL COMPOUNDS - IDENTIFICATION

Method 1 strong peak around 1400-1600 cm-1 in the infra red spectrum

Method 2 formation of an orange precipitate with 2,4-dinitrophenylhydrazine

Although these methods identify a carbonyl group, they cannot tell the difference
between an aldehyde or a ketone. To narrow it down you must do a second test.
 CARBONYL COMPOUNDS - IDENTIFICATION

Differentiation to distinguish aldehydes from ketones, use a mild oxidising agent

Tollen’s
Reagent ammoniacal silver nitrate
mild oxidising agent which will oxidise aldehydes but not ketones
contains the diammine silver(I) ion - [Ag(NH3)2 ]+
the silver(I) ion is reduced to silver Ag+(aq) + e¯ ——> Ag(s)
the test is known as THE SILVER MIRROR TEST
 CARBONYL COMPOUNDS - IDENTIFICATION

Differentiation to distinguish aldehydes from ketones, use a mild oxidising agent

Tollen’s
Reagent ammoniacal silver nitrate
mild oxidising agent which will oxidise aldehydes but not ketones
contains the diammine silver(I) ion - [Ag(NH3)2 ]+
the silver(I) ion is reduced to silver Ag+(aq) + e¯ ——> Ag(s)
the test is known as THE SILVER MIRROR TEST

Fehling’s
Solution contains a copper(II) complex ion giving a blue solution
on warming, it will oxidise aliphatic (but not aromatic) aldehydes
the copper(II) is reduced to copper(I)
a red precipitate of copper(I) oxide, Cu2O, is formed

The silver mirror test is the better alternative as it works with all aldehydes

Ketones do not react with Tollen’s Reagent or Fehling’s Solution

 CARBONYL COMPOUNDS - CHEMICAL PROPERTIES

OXIDATION

• provides a way of differentiating between aldehydes and ketones

• mild oxidising agents are best
• aldehydes are easier to oxidise
• powerful oxidising agents oxidise ketones to a mixture of carboxylic acids

ALDEHYDES easily oxidised to acids

RCHO(l) + [O] ——> RCOOH(l)

CH3CHO(l) + [O] ——> CH3COOH(l)
 Common aldehydes and ketones
• Aldehydes are often recognizable by their “sweet” smells:

Benzaldehyde Cinnamaldehyde
(almond flavoring) (cinnamon flavoring)
Vanillin
(vanilla flavoring)
 Common aldehydes and ketones
• Some ketones (e.g. acetone) have a “sweet” smell also). Other
examples are:

2-Heptanone Butanedione
(clove flavoring) (butter flavoring) Carvone
(spearmint flavoring)
Naturally occurring aldehydes and ketones
Testosterone

• A wide variety of
biologically relevant
molecules possess
aldehyde and/or ketone Progesterone

functional groups:

Cortisone

D-Glucose
 Identify the Compounds

3-Pentanone 2-Pentanone
Propanone Propanal
C5H10O
C3H6O

2-Pentanone
3-Methyl-2-butanone
C5H10O
 Nomenclature of
IUPAC System Aldehydes
o Aliphatic aldehydes are named by dropping the suffix -e from the name of the hydrocarbon that has
the same carbon skeleton as the aldehyde and replacing it with the suffix -al.
Alkane - e+ al = Alkanal

o Substituted aldehydes, we number the chain starting with the aldehyde carbon.
▪ -CH=O group is assigned the number 1 position.
▪ Aldehyde group has priority over a double bond or hydroxyl group.

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 Nomenclature of
IUPAC System Aldehydes
o Cyclic aldehydes, the suffix –carbaldehyde is used.

o Aromatic aldehydes are usually designated as derivatives of the simplest aromatic aldehyde,
benzaldehyde.

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 Nomenclature of
Common Names Ketones
o Common names of ketones are formed by adding the word ketone to the names of the alkyl or aryl
groups attached to the carbonyl carbon. Alkyl ketone.

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 Nomenclature of
IUPAC System Ketones
o In the IUPAC system, the ending for ketones is -one.
o The chain is numbered so that the carbonyl carbon has the lowest possible number.
o For cyclic ketones, numbering always starts from the C=O group.
o The prefix "oxo" is used when the ketone is not the principal functional group.

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 Nomenclature of
NOTES Aldehydes and Ketones
o In common names carbon atoms near the carbonyl group are often designated by Greek letters.
o The atom adjacent to the function is alpha (α), the next removed is beta (β) and so on. Since
ketones have two sets of neighboring atoms, one set is labeled α, β etc., and the other α', β' etc.

o The functional group priority order in nomenclature system is as following:

Acid and derivatives >aldehyde> ketone> alcoho > amine > alkene > alkyne > ether
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Physical Properties of Aldehydes and Ketones
o Boiling Points
▪ Carbonyl compounds boil at higher temperatures than hydrocarbons, but at lower temperatures
than alcohols of comparable molecular weight.

▪ This is due to the intermolecular forces of attraction, called dipole-dipole interactions, which is
stronger than van der Waals attractions but not as strong as hydrogen bonds.

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Physical Properties of Aldehydes and Ketones
o Solubility
▪ Carbonyl compounds as aldehydes and ketones have a C=O bond, but no O-H bond, cannot
form hydrogen bonds with themselves.
▪ The polarity of the carbonyl group also affects the solubility properties of aldehydes and
ketones.
▪ Carbonyl compounds with low molecular weights are soluble in water as they can form
hydrogen bonds with O-H or N-H compounds.

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Preparation of Aldehydes and Ketones
1) Oxidation of Primary and Secondary Alcohols

2) Hydration of Alkynes
Hydration of terminal alkynes EXCEPT acetylene yields ketones (catalyzed by acid and mercuric).

3) Ozonolysis of Alkenes

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Preparation of Aldehydes and Ketones
4) Friedel-Crafts Acylation
Preparing ketones that contain an aromatic ring.

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Reactions of Aldehydes and Ketones
A) Reduction of Carbonyl Compounds
o Aldehydes and ketones are easily reduced to primary and secondary alcohols, respectively.
o The most common metal hydrides used to reduce carbonyl compounds are lithium aluminum
hydride (LiAlH4) and sodium borohydride (NaBH4).

B) Oxidation of Carbonyl Compounds

o Oxidation of aldehydes gives a carboxylic acid with the same number of carbon atoms.
o Because the reaction occurs easily, many oxidizing agents, such as KMnO4, CrO3, Ag2O and
peracids will work.

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Reactions of Aldehydes and Ketones
C) Nucleophilic Addition Reactions
o Nucleophiles attack the carbon atom of a carbon-oxygen double bond because that carbon
has a partial positive charge.
o The overall reaction involves addition of a nucleophile and a proton across the pi bond of the
carbonyl group (when carried out in alcohol or water).

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 Reactions of Aldehydes
C) Nucleophilic Addition Reactions and Ketones
1) Addition of Grignard Reagents: Formation of Alcohols
o Grignard reagents act as carbon nucleophiles toward carbonyl compounds.
o The reaction of a Grignard reagent with a carbonyl compound provides a useful route to alcohols.

o The type of carbonyl compound chosen determines the class of alcohol produced.

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 Reactions of Aldehydes
C) Nucleophilic Addition Reactions and Ketones
1) Addition of Grignard Reagents: Formation of Alcohols
o Formaldehyde gives primary alcohols.

o Other aldehydes give secondary alcohols

o Ketones give tertiary alcohols.

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 Reactions of Aldehydes
C) Nucleophilic Addition Reactions and Ketones
2) Addition of Hydrogen Cyanide: Formation of Cyanohydrins
o Hydrogen cyanide adds to the carbonyl group of aldehydes and ketones to form cyanohydrins,
compounds with a hydroxyl and a cyano group attached to the same carbon.

o Example

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 Reactions of Aldehydes
C) Nucleophilic Addition Reactions and Ketones
3) Addition of Alcohols: Formation of Hemiacetals and Acetals
o Alcohols add to the C=O bond, the OR group becoming attached to the carbon and the proton
becoming attached to the oxygen.
o Aldehydes and ketones react with alcohols to form, first, hemiacetals and then, if excess alcohol
is present, acetals.

o Hemiacetals; it contains both alcohol and ether functional groups on the same carbon atom.

o Acetals have two ether functions at the same carbon atom.

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 Reactions of Aldehydes
C) Nucleophilic Addition Reactions and Ketones
3) Addition of Alcohols: Formation of Hemiacetals and Acetals
o The reverse of acetal formation, called acetal hydrolysis.
o Acetal can be hydrolyzed to its aldehyde or ketone and alcohol components by treatment with
excess water in the presence of an acid catalyst.

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 Reactions of Aldehydes
C) Nucleophilic Addition Reactions and Ketones
4) Addition of Ammonia and Ammonia Derivatives
The addition of nitrogen nucleophile, such as ammonia(NH3) and substituted ammonia (NH2-Y).

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