MINISTRY OF PUBLIC HEALTH

ZAPOROZHYE STATE MEDICAL UNIVERSITY

DEPARTMENT OF ORGANIC AND BIOORGANIC CHEMISTRY

LECTURE:
CARBONYL
COMPOUNDS.
CARBOXYLIC ACIDS.
LIPIDS.

Lecturer:
Assistant professor Antypenko Lyudmyla Mykolaivna
 Plan
Part I Part II

1. Classification of aldehydes 1. Classification of carboxylic acids

and ketones. 2. Nomenclature.
1. Nomenclature. 3. Preparation methods.
2. Preparation methods. 4. Chemical properties:
3. Chemical properties:  reactions by acidic О–Н;
 nucleophilic addition;  nucleophilic substitution;
 addition – elimination;  hydrogen at α-Carbon substitution;
 condensation;  oxidation and reduction.
 at -Carbon; 5. Medical usage.
 polymerisation; 6. Esters. Structure and chemical
 oxydation and reduction properties.
5. Aldehydes and ketones in 7. Lipids. Structure and physico-
medicine . chemical properties.

2
Aldehydes and ketones
A carbonyl group is a group of carbon atom double-bonded to an
oxygen atom.

O
Aldehydes is organic compounds in which
R C carbon atom of the carbonyl group is bonded
to a hydrogen atom.
H
O
Ketones - organic substances, the molecules of
which contain a carbonyl group bonded with two
hydrocarbon radicals.
C
R R'
3
Aldehydes and ketones
Classification
Aldehydes, ketones

aliphatic O
H3C
saturated H
Acetaldehyde

unsaturated H
Propenal 4
Aldehydes and ketones
Classification
Aldehydes, ketones

aromatic Alicyclic
(aliphatic cyclic)

O H O H

Benzaldehyde Cyclohexanecarbaldehyde 5
Aldehydes. Nomenclature.
Trivial
Substitutive
(Common name)

O
methanal H C formic aldehyde,
formaldehyde
H

O
acetic aldehyde,
ethanal CH3 C acetaldehyde
H

6
Aldehydes. Nomenclature.
Trivial
Substitutive
(Common name)
O
H3C H2C CH2 C butyric aldehyde,
butanal H butylaldehyde

O
H3C H2C H2C CH2 C valerianic aldehyde
H valerialdehyde
pentanal
    O
CH3 CH2 CH2 CH C
CH3 H
7
-methylvalerianic aldehyde
Ketones. Nomenclature.
Radicalo-functional Substitutive Trivial

CH3 C CH3
O
dimethylketone propan-2-one acetone

5 4 3 2 1
CH3 CH CH2 C CH3
CH3 O

4-methylpentan-2-one 8
Preparation methods:
1. Alcohols oxidation:

[O] O
R CH2 OH R C
- H2O
Primary alcohols aldehydes
H

R CH R' [O]
R C R'
- H2O
OH O
9
Secondary alcohols ketones
Preparation methods:
2. Alkynes’s hydration (Kucherov’s reaction)

10
Preparation methods:
3. Heminal dihalogenalkanes’s hydrolysis

Cl O
H2O
CH3 CH2 CH CH3 CH2 C + 2 HCl
Cl H
1,1-Dichloropropane Propionaldehyde

11
Preparation methods:
4. Pyrolysis of carboxylic acids salts

O
CH3 C
O 3000 C
O
Ca CH3 C + CaCO3
O H
H C
O
12
 Structure and chemical properties
123,8o
.. Trigonal planar structure.
122,4o C O ..
The bond angles are about 120°

0,122 í ì
- '+
+ O R C R
R C
The electronegativity of oxygen is
H O '- much greater than that of carbon .

+ > '+
The double bond is polarized: the oxygen atom acquiring a fractional
negative charge (δ-) and the carbon atom - a fractional positive charge (δ+).

Because donating influence of two hydrocarbon chains at carbonyl 13

Carbon, ketones are less reactive than aldehydes.
Chemical properties.

Í
-
 + O Electrophilic
R C C center
H
Í
CH-acidic center

14
Chemical properties.
Characteristic reactions are:

 nucleophilic addition;
 addition – elimination;
 condensation;
 at -Carbon;
 polymerisation;
 oxydation and reduction

15
Chemical properties.
Í
-
 + O
Tautomerism R C C
H
Eltekov rule: Í
Enols (unsaturated aliphatic hydrocarbons containing a hydroxyl group at a
carbon-carbon double bond) are unstable and, at the time of formation, convert
into isomeric carbonyl compounds — aldehydes and ketones.

16
 Chemical properties.
Nucleophilic addition (AN)

1. Addition of cyanic acid.

O- -
+ + - CN
CH3 C + H CN CH3 CH CN
H
OH
2-hydroxypropanenitrile

17
Chemical properties..
Nucleophilic addition (AN)
2. Addition of alcohols
OH +
O H
R C + R' OH R C OR'
H
H
hemiacetal
+ OR'
H
R C OR' + H2O
H 18
acetal
Chemical properties.
Addition – elimination reaction (AN-E)
1. Shiff bases formation

C O + H2N R

C N R + H2O
19
azomethins
 Chemical properties.
Addition – elimination reaction (AN-E)
2. With hydroxylamine

O R CH N OH + H2O
R C + H2N OH
H
aldoxime
R C R' + H2N OH R C R' + H2 O
O N OH

ketoxime 20
Chemical properties.
Addition – elimination reaction (AN-E)
3. With hydrazine derivatives
R
C O + H2N NH
R'
phenylhydrazine

R
C N NH + H2O
R' 21
phenylhydrazone
Chemical properties.
Reactions at α–Carbon
1. Halogenation
O
CH3 CH2 C + Br2
H
+
H O
CH3 CH C + HBr
H
Br 22
α-bromopropionic aldehyde
 Chemical properties..
Reactions at α–Carbon
2. „Iodoform test”
basic conditions → keto-enol tautomerization. → electrophilic attack of enolate
by the hypohalite → α position exhaustively halogenated → a
nucleophilic acyl substitution by hydroxide → −CI3 anion abstracts a proton from
the solvent → formation of the iodoform.

O O
3I2, NaOH
R C CH3 R C CI3

NaOH
RCOONa + CHI3

Iodoform is a pale-yellow solid (high molar mass of the three iodines). 23

 Chemical properties..
Reactions at α–Carbon
3. Aldol-crotonic condensation

 O  O
H CH C + OH- CH C + HOH
H H
R R

 O
O H2O
CH3 C CH C
H +
H -OH-
H 24
Chemical properties.

OH
H2O O to
CH3 C CH2 C
-OH- H -H2O
H
3-hydroxybutanal
O
CH3 HC CH C
H
crotonic aldehyde 25
Chemical properties.

4. Cannicaro reaction

O KOH
2 H C
H
O
H C + H3C OH
OK
potassium methylate methanol 26
Chemical properties.

5. Reduction
O LiAlH
4
CH3 CH2 C
H

CH3 CH2 CH2 OH

27
Chemical properties.

6. Oxydation
O
R C + 2 [Ag(NH3)2]OH
H
Tollen’s reagent
O
2Ag + R C +
ONH4
+ 3NH3 + H2O 28
 Chemical properties..

7. Oxidation
COOH NaOOC
HC O HO CH O
2 Cu 3NaOH, 2KOH
+ CH3 C
HC OH O CH
H
COOK HÎ ÎC
Felling’s reactive
COOK
O HC OH
CH3 C + 2CuOH+ 2 H2O + 2
- + HC OH
ONa
COONa
t 29
2CuOH Cu2O + H2O
 Chemical properties..

The oxidation of ketones takes place only in the

presence of strong oxidizers (KMnO4, K2Сr2O7 etc.)

[O] O O
CH3 C CH2 CH3 H C + CH C
3
O OH OH
O
+ CH3 CH2 C
OH
30
 Aromas of aldehydes and ketones

β-Damascenone

Anisaldehyde

31
2-acetyl-1-pyrroline
Ionons
Aldehydes and ketones

Testosterone Progesterone
Vanillin

Menton 32

Cinnamaldehyde
Carboxylic acids - derivatives of hydrocarbons,
containing in the structure the one or more carboxyl
groups – COOH.
Classification
• nature of hydrocarbon radical

aliphatic aromatic alicyclic

saturated unsaturated O O
O O C C
CH3 C H2C CH C OH OH
OH OH
• number of groups – СООН

monocarboxylic dicarboxylic
O O O
H C C CH2 C
33
OH HO OH
Carboxylic acid. Nomenclature.
O O 4 3 2 1 O
H C CH3 C H3C H2C CH2 C
OH OH OH

substitutive methanoic ethanoic butanoic acids

methane 1-propane
rational carboxylic acid carboxylic acid

trivial formic acid acetic butyric

34
Preparation methods:
1. Oxidation of primary alcohols and aldehydes

2. Hydrolysis geminal trihalogen derivatives

3. Carboxylation of organomagnesium compounds

CO2 O HCl O
C2H5 MgCl C2H5 C C2H5 C
- MgCl2
OMgCl OH

35
Preparation methods:
4. Hydrolysis of nitriles

H2O (OH- или H+) O H2O (OH- или H+) O

R C N R C R C
NH2 - NH3 OH
nitril amide

5. Hydrocarbonylation of alkenes

H+, p, t
H2C CH2 + CO + H2O CH3 CH2 COOH

36
Chemical properties

H ..
O electrophilic center
 +
..
R C C
..
СН-acidic O
.. H '+ ОН-acidic center
H
center ''+

• Reactions by acidic О–Н

• Nucleophilic substitution;
• Hydrogen at α-Carbon substitution;
• Oxidation and reduction.
37
37
Chemical properties
1. Acidic properties

O O
H3C C + H2O H3C C + H3O+
O H O

.. - -1/2
O O O
R C R C or R C
.. -
O O O -1/2

H COOH CH3 COOH Cl CH2 COOH

pKa 3,75 pKa 4,76 pKa 2,75 38
Nucleophilic substitution reactions (SN)

1. The esterification reaction

O
CH3 C H2SO4 O
OH + H OC2H5 CH3 C + H2O
OC2H5
2. Halogenation

O
SOCl2
CH3 COOH CH3 C + SO2 + HCl
Cl

39
39
 Esters - a group of fragrant substances that are components of fruit essences.

O O O
H3C H2C H2C C CH3
H3C C CH3 H3C C
O CH2 CH2 CH
O CH2 CH2 CH O CH2 7
CH3
isoamylbutyrate CH3
CH3
isoamylacetate octylacetate

O
O H
O
O

butyric acid ethyl ester formic acid isobutyl ester 40

40
 Nucleophilic substitution reactions (SN)
3. Formation of acid anhydrides

O
P2O5
2 CH3 C CH3 C O C CH3
-H3PO4
OH O O

acetic anhydride

4. Reaction with ammonia and amines

O O O
200oC
H3C C + NH3 H3C C H3C C
+ - H2O
OH O NH4 NH2

ammonia acetate acetamide

41
41
4. Oxidation and reduction

O O
NH4OH
+ Ag2O HO C + 2Ag
H C
OH OH

CO2 + H2O

O [H] O [H]
R C R C R CH2 OH
OH H
42
42
 Dicarboxylic acids
Nomenclature
O O O O O O
C C C CH2 C C H2C CH2 C
HO OH HO OH HO OH

Subsitutive ethandioic propandioic butandioic

Trivial oxalic malonic succinic

43
43
Rumex acetosa
Succinum
Óxalis Acidum malicum
 Heating of the dicarboxilic acids
200 oC
HOOC COOH H COOH + CO2
formic acid

150 oC
HOOC CH2 COOH CH3 COOH + CO2
acetic acid
O O
C 300 oС C
H2C O H H2C
- H2O O
H2C OH H2C
C C
O O
succinic anhydride
O O
H2C C H2C C
O H 300 oС
H2C - H2O H2C O
OH
H2C C H2C C
O O 44
44

glutaric anhydride
Lipids (fats) - are esters, that are formed of the trihydric alcohol glycerol
and higher fatty acids.

45
In triacylglycerol residues of animal origin predominate saturated acids.
Usually they have a solid consistency.

Liquid vegetable oils contain mostly

unsaturated acids residues.

46
Hydrogenation of fats - the process of adding hydrogen to unsaturated
acids contained in the fat. As a result, liquid fats into solid.

O O
CH2 O C C17H31 CH2 O C C17H35
O O
CH O C C17H33 8[H]
Ni CH O C C17H35
O O
CH2 O C C17H33 CH2 O C C17H35

47
 Saponif ication ( hydrolysis) of f ats
CH2 OH C17H33COOН
oleinic acid
CH OH +
O 2C17H35COOН
CH2 O C C17H33 CH2 OH stearinic acid
O
CH O C C17H35
O
CH2 O C C17H35 CH2 OH C17H33COONa
sodium oleonate
CH OH +
2C17H35COONa
CH2 OH sodium stearate

48
 Iodine number - an indicator of unsaturated fat.

O O I I
CH2 O C C17H33 CH2 O C (CH2)7 CH CH (CH2)7 CH3
O O
CH O C C17H35 + I2 CH O C C17H35
O O
CH2 O C C17H31 CH2 O C C17H31

49
Phospholipids - lipids containing phosphoric acid.
The most common ester among glycerophospholipids are
phosphoglycerides - phosphatides, which are derivatives of
L-phosphatidic acid.

In natural phosphatides residue at C1 is saturated acid,

at C2 - unsaturated acid residue,
and one of the hydroxyls is esterified with a phosphoric acid or a
polyhydric alcohol aminoalcohol.
O
1
CH2 O C C17H35
O
2
C17H33 C O CH
O
3 CH O P OH
2
OH
50
L-phosphatidic acid
Representatives of phosphatides are cephalins - containing amino alcohol
colamine.

The complete hydrolysis of the kephaline molecule gives glycerine, two

molecules of higher fatty acids, phosphoric acid and the molecule of
colamine.
O
CH2 O C C17H35
+ C17H35COOH
O + CH2 OH
4HOH, H
C17H33 C O CH CH OH + C17H33COOH
O CH2 OH
CH2 O P O CH2 + H3PO4 + HO CH CH NH
2 2 2
O- CH2
NH3+

phosphatidylethanolamine

51
 Lecithins - phosphatides containing aminoalcohol choline.

O
CH2 O C C17H35
+ C17H35COOH
O + CH2 OH
HOH, H
C17H33 C O CH CH OH + C17H33COOH
O CH2 OH
CH2 O P O CH2 CH2 + H3PO4 +
CH3
O- H3C N CH3
[ HO CH2 CH2 N CH3 ]OH-
CH3
CH3
52
Thank You
for Your
attention!

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