Aldehydes, Ketones, and

carboxylic acids
 O Aldehydes
R  The term Aldehyde come for the
words alcohol dehydrogenation.
H
Carbonyl group
 Preparation: Oxidation of primary alcohols
according to the following equation:
R R
OH + [O] O

 Note: Oxidation can be considered as removal of hydrogens.

 [O] can be obtained from oxidazing agents such as
KMnO4,KCr2O7,CuO.
 Aldehydes
 Examples:
OH O
H + [O] H
Methyl alcohol H Formaldehyde H

OH O
H 3C + [O] H 3C
Ethyl alcohol H Acetaldehyde H

C H3 O H

+ [O]
Toluene Benzaldehyde
 Aldehydes
Note:
 The formation of acetaldehyde in the liver is
partailly responsible for liver cirrhosis.

 The formation of formaldehyde and ist oxidation

product formic acid are responsible for the
systematic toxicity of methyl alcohol
(methanol).

 The side chain in toluene is more susceptible to

oxidation than the benzne ring.
 IUPAC Nomenclature of Aldehydes
 The aldehyde group is always at the end of the chain
(carbon 1)
 Aldehydes end in al
 Take the name of the longest chain cotaining the
aldehyde group
 Drop the ending e and replace it by al
Br CH3
H3C O H3C O

H3C H3C Cl Br

6-bromo-5,7-dimethyloctanal 3-bromo-5-chloro-4-methylhexanal
IUPAC Name Common Name

Methanal Formaldehyde

Ethanal Acetaldehyde

Propanal Propionaldehyde

2-Methylpropanal Isobutyraldehyde
 Uses of aldehydes
O
O H

O
H
H OCH3
OH
Formaldehyde Vanillin Cinnamic adehyde
 40% Formaldehyde in water (Formalin): used for
disinfection of excerta, rooms, clothing (Mechanism:
hardening of proteins), in embalming (‫ )ا لتحنيط‬water,
and as preservative for biological specimens.
 Benzaldehyde: preparation of flavoring agents,
parfums, drugs, and dyes.
 Vanilllin (Vanilla beans) and cinnamic aldehyde
(cinnamon bark): flavoring agents.
 Tests of aldehydes

 Adehydes are good reducing agents.

 Glucose contains an aldehyde group. Therefore, it can
react as an aldehyde, and can be detected in urin using
special solutions such as Benedicts, Fehlings, or Tollens
reagent.
 Reactions of aldehydes

 Oxidation:  Acid
O O
R + [O] R
H O H
 Reduction:  Alcohol
O OH
R + [H] R
H H
Examples:
H 3C
H 3C O + [H]
Ethanal Ethanol O H
O O H

+ [H]

Benzaldehyde Benzylalcohol
 Reactions of aldehydes

 Biological oxidation-reduction reactions in

the are crried out in the body by substances
called coenzymes. One coenzyme is NAD+
(Nicotinamide Adenine Dinucleotide)

H3C OH + NAD+ H3C O + NADH

 Ketones
 Secondary alcohol  oxidation  ketone
H3C CH3
H3C CH3 + [O]
O
HO
Isopropyl alcohol Acetone
2- Propanol Propanone
Cl
O CH3
O
Cl

Acetophenone Chloracetophenone (tear gas)

 Naming of Ketones
IUPAC
 Aldehydes end in -one
 Take the name of the longest chain
 Drop the ending e and replace it by -one
Common
 Each alkyl group attached to the carbonyl group is
named and the word ketone is added afterward.

O H3C CH3
H3C Cl
CH3
Cl O
3-Hexanone
Ethylpropylketone 4,4-dichloro-2-pentanone
 Uses of Ketones
 Acetone is a good solvent for fats and oils
(previuosly used in finger nail polish).
 Present in small amounts in blood and urine (in
normal individuals).
 Present in large amounts in blood and urine and
expired air in case of untreated diabetes mellitus.
 Dihydroxy acetone is an intermediate in
carbohydrate metabolism.
O O
HO OH
H3C CH3
Acetone Dihydroxy acetone
 Reactions of ketones

 Ketones are usually unreactive.

 Ketones are not easily oxidized.
 They can however be reduced to the
corresponding secondary alcohols.
 Ketones give negative tests with oxidazing
agents such as Benedict‘s reagent. However
aldehyde give positive results with these
reagents.
 Reactions of ketones
Hemiacetals and Hemiketals

How can an acetal or a ketal be formed?

Importance:
Hemiketal / acetal  monosaccharides
Ketal / Acetal  Di- and Polysaccharides
 Carboxylic acids
Preparation
Oxidation of aldehydes
HO
O + [O] O
H3C H3C
Acetaldehyde Acetic acid

O H O O

+ [O]

Benzaldehyde Benzoic acid

 Stepwise oxidation of a primary alcohol carboxylic acid

H 3C O H + [O] H 2 C O + [O]
Methylalcohol Formaldehyde
O
HO
Formic acid

 Direct oxidation of primary alcohols  acids

HO
OH O
H3C + [O]
H3C

Ethyl alcohol Acetic acid

 Naming of carboxylic acids
IUPAC Names
 Carboxylic acids end in –oic acid
 Take the name of the longest chain cotaining the
acid group.
 Drop the ending e and replace it by -oic
Common Names
 Derived from the names of the aldehyde forms from
which they may be prepared
HO
O
H3 C
Ethanoic acid Carboxyl group which yields
Acetic acid hydrogen ions
 Naming of carboxylic acids
 Dicarboxylic, and tricarboxylic acids are carboxylic acids
which contain two and three carboxylic acids,
respectively.
O O Ethanedioic aic
Oxalic acid O OH
O O
HO OH

Propanedioic acid HO OH
O O OH
Malonic acid
HO OH Citric acid

O O
Butanedioic acid
Succinic acid
HO OH
 Naming of carboxylic acids
Examples:
H3C O
H3C
OH
CH3 Cl
2-chloro-3,4-dimethylheptanoic acid

HO O

Cl

Br
4-bromo-2-chlorobenzoic acid
 Properties and Reactions of Carboxylic acids
 Weak acids
O O
H3C H+ + H3C
OH O-
Hydrogen Acetate ion
Acetic acid ion

 React with bases to form salts and water

O O
H3C + NaOH H3C + H2O
- +
OH O Na

CH3CHOOH + NaOH CH3CHOONa + H2O

 Properties and Reactions of Carboxylic acids
 React with bases to form salts and water

CH3CHOOH + NaHCO3 CH3CHOONa + CO2 + H2O

Sodium
bicarbonate

2 HCOOH + Na2CO3 2 HCOONa + CO2 + H2O

Formic acid Sodium Sodium
carbonate formate

 Their solubility in water decreases as the length

of their carbon chains increases
 React with alcohols to form esters
 Medically important acids
 Magnesium citrate  cathartic (evacuation of bowel)
 Sodium Citrate  anticoagulant (removel of Ca2+ needed for
coagulation
 Lactic acid results from fermentation of milk sugar (lactose)
[lactic acidboth acid and alcohol)
 Lactic acid is formed by anarobic energy production in the
body from Pyruvate (muscle exercise)
 Pyruvic acid is formed during anarobic phase of glucose
oxidation
 Pyruvic acid  acetyl CoA  Krebs cycleEnergy production
OH O
O O
H3 C H3C
OH OH
Lactic acid Pyruvic acid
 Medically important acids
 Oxalic acid  removal of strains, from clothing, prevention of
blood clotting (Note: Oxalic acid is a poison if taken internally)
 Stearic acid (C18) is a fatty acid, insoluble in water, ist salt is
used as in Soap
 Bezoic acid antifungal; sodium salt  preservative
 Salicylic acid (both alcohol and acid) removal of warts and
corns
Acetylsalicylic acid (Aspirin):
analgesic, antipyretic, aginst
O OH HO O
rheumatic fever (‫)ا لحمىا لروماتيزمية‬,
prevention of blood clots from OH O CH3
forming (Note: contraindicated
after Surgery) helps in O
preventing heart attacks,
bleeding of stomach (not to be Acetylsalicylic
taken on empty stomach) Salicylic acid
acid