CHE 176
ORGANIC CHEMISTRY I
PROFESSOR S. A. ABOABA
OFFICE: F106, CHEMISTRY DEPT.
OUTLINE
CARBONYL COMPOUNDS (ALDEHYDES & KETONES)
CARBOXYLIC ACIDS AND DERIVATIVES
BRIEF INTRODUCTION TO BIO-MOLECULES (CHO, PROTEINS)
SYNTHETIC POLYMERS
INTRODUCTION TO SPECTROSCOPY (IR, UV, NMR, MS)
BASIC CONCEPT OF ORGANIC SYNTHESIS
CARBONYL COMPOUNDS
•Aldehydes and ketones are usually referred to as carbonyl
compounds.
•There are other organic compounds with the carbonyl functional
group. These include carboxylic acids, esters, acid halides, acid
anhydrides and amides.
ALDEHYDES AND KETONES
• The functional group of aldehydes and ketones is the carbonyl group
and it is denoted as:
• Aldehydes have the general formula
• While ketones are being represented by R can be alkyl or
aryl.
• The presence of the highly reactive carbonyl group indicates the
similarities in the chemical reactions of the two class of compounds
although there are certain aspects where they differ.
• Saturated aliphatic aldehydes are referred to as alkanals
NOMENCLATURE
• According to the IUPAC system of naming compounds, the name of
an aldehyde is obtained by replacing the terminal “e” in the
corresponding alkane with the suffix “al”
• The aldehydic functional group - always occur at the end of
chain, and remember that you always give the smallest number
possible to the functional group.
• When other functional groups are present in the compound, their
positions are specified with numbering.
Aldehydes
O CH3 C2H5
H3C
H H3C
H3C CHO
Cl
2-methylpropanal 3-chloro, 2-ethyl, 4-methyl, pent-3-enal
O H
Propanal
Benzaldehyde or phenyl methanal
Ketones
• Ketones are named by adding the suffix “one” to the name of
the corresponding alkane, the carbon atom of the carbonyl
group will bear the smallest possible number.
O O
H3C CH3 H3C CH3
Proapnone 2-pentanone
Take Home Assignment
Draw the structures of the following compounds:
(i)pentanal
(ii)3-chlorobutanal
(iii)2-methyl-2,butenal
(iv)phenylethanal
(v)4-methylpentanal
(vi) 4-chlorobenzaldehyde.
(vii)Phenylethanone(acetophenone)
(viii) diphenylmethanone(benzophenone)
Importance, Uses and Applications of some Aldehydes
Methanal
• Industrially as a reactant in the synthesis of polymers in production of plastics, carpets,
fabrics, insulators, and some other domestic materials.
• 40% methanal is an active germicide, disinfectant, used in preservation of biological
specimen, called ‘formalin
Ethanal
• production of ethanoic acid and its derivatives
Benzaldehyde: Naturally occurring pleasant smelling benzaldehyde and derivatives in food
flavour and fragrances in perfumes
• benzaldehyde in almond;
• vanillin [3-methoxy, 4-hydroxy-benzaldehyde] in vanilla beans
• cinnamaldehyde [3-phenyl-2-propenal] in cinnamon.
Importance, Uses and Applications of some Ketones
Propanone (acetone) as solvent; in rubber cement and paints, and as
nail-polish removers. The body produces propanone during fasting, in
uncontrolled diabetes, and high-protein diets when large amounts of
fats are metabolized for energy.
Butadione - One of the unappealing odor of armpits and sweaty feet
Carvone - Flavour compound in oil of spearmint
Menthone in flavouring
Muscone (in musk perfumes)
Cyclohexanone - intermediate in manufacturing of other chemicals;
used in one stage of nylon production.
Practice Questions
1. Write the IUPAC name of the following structures:
O H3C Cl Br
H3C H3C
CH3 CH3
H3C H3C CH3 H3C
Br O Br CH3
H3C O
2. Draw the structures of:
(i)phenylethanone[acetophenone]
(ii) diphenylmethanone [benzophenone]
FEATURES OF CARBONYL GROUP
• The carbonyl group: It is made of carbon and oxygen double bonds. The
double bond has a dipole, unlike double bond in alkenes. i.e.
-
O
+
C
R R
The carbonyl carbon is bonded to three other atoms using the three sp2
hybridisation separated approximately by 1200. The unaffected p-orbital of
carbonyl carbon overlaps with p-orbital of the oxygen atom to form a pie
(π) bond. The pie (π) bond is distorted towards the more electronegative
oxygen atom. The carbonyl carbon and oxygen with the two other atoms
bonded to C=O all lie on same plane i.e. it is FLAT.
Carbon and oxygen have different electronegativities. Therefore,
the electrons are not shared equally in the C=O. The pi (π)
electrons spend longer time with more electronegative oxygen
than carbon. This results in a form of partial polarities and affects
the chemistry and reactions of carbonyl compounds.
The carbon atom in C=O is slightly electron deficient. Hence electron-
rich reagent (Z:) – nucleophile (bases) easily form bonds with the
carbonyl carbon. Therefore, as nucleophile approach the carbonyl
bond, it bonds to the electron deficient carbon. This is responsible for
the general “Nucleophilic Addition Reactions” of the carbonyls. The
flat shape of trigonal (C=O) group makes it possible to be attacked
from below or above its plane of symmetry.
GENERAL METHODS OF PREPARATION
Recall!!!
Primary alcohol 10, secondary alcohol 20, and tertiary alcohol 30
respectively gives the following on oxidation
•Primary alcohol[RCH2-OH]Aldehyde[RCHO] carboxylic acid [RCOOH].
•Secondary [20] alcohol [RR1CH-OH] Ketone [RR1CO].
•Tertiary [30] alcohol [RR1R11C-OH] No reaction
GENERAL METHODS OF PREPARATION CONTD.
1. OXIDATION OF ALCOHOLS:- Aldehydes and ketones can be
respectively prepared by the controlled oxidation of primary and
secondary alcohols respectively using an acidified solution of
potassium dichromate or permanganate.
2. DRY DISTILLATION:- Calcium salt of carboxylic acid can undergo dry
distillation with calcium formate to form aldehyde. Dry distillation
of the calcium salt alone could yield ketone.
3. REDUCTION OF ACID CHLORIDES:- Acid chlorides can be reduced
using Lithium aluminium hydrogen tritertiary butoxide followed
by acid hydrolysis. It is a mild reducing agent when compared
with lithium aluminium hydride which will have reduced the
carbonyl functional group.
PROPERTIES OF CARBONYL COMPOUNDS
A. Physical Properties
• Methanal (lowest aldehyde) is gas at room temperature while and other
aliphatic aldehydes and ketones of lower relative molecular mass (r. m. m)
are liquids.
• Carbonyls have boiling points slightly lower than those of alkanes of
comparable r. m. m due to the polarity of the carbonyl group.
• Lower mwt. Aldehydes and ketones are completely miscible with water
(solubility decreases from the 5-carbon compound upwards).
• Their solubility in water can be explained in terms of the dipole moment
which causes attraction between the partially positive charged carbon (C=O)
and the oxygen of O-H in water and the hydrogen bond between the oxygen
of the polar bond and water molecule.
• For aromatic carbonyl compounds, the 1st member (benzaldehyde) and the
simplest ketone (phenyl ethanone) are liquids.
IMPORTANT TO NOTE
Polarity of the carbonyl group in aldehydes and ketones is responsible
for the observed higher boiling points of these compounds compared
to their non-polar molecular weight equivalents. NB: But they do not
form intermolecular hydrogen bondings [as in alcohols and carboxylic
acids], hence they have lower boiling points compared to alcohols and
carboxylic acids of equivalent weight.
B. Chemical Properties
The carbonyl functional group is one of the most reactive groups
organic chemistry. It is based on the high polarity of the C=O which
leaves the carbon atom electron-deficient and hence susceptible to
attack by nucleophiles. Most reaction of aldehydes and ketones are
addition reaction leading to the formation of –OH.
Ease of nucleophilic attack on carbon atom
HCHO > RCHO > RCOR > ArCHO > ArCOR > ArCOAr
This is because the R-group releases electrons by inductive effect while
Ar-group releases electrons by mesomeric effect.
Nucleophilic Addition Reactions
a. Addition of Hydrogen Cyanide (it is a method used for making mixed acids and alcohols)
Cyanohydrins can be hydrolysed to α-hydroxyl acid
Mechanism:
b. Addition of Sodium bisulphite
The reaction with sodium bisulphite to form bisulphite addition compound
proceeds by an analogous mechanism as cyanide addition.
[(S:) lone pairs of e- on the sulphur attacks the carbonyl carbon]
c. Addition reaction with Grignard Reagents
d. Condensation (addition-elimination) Reaction with Derivatives of
ammonia – Aldehydes and ketones react with amino-group to give compounds containing the
C=N linkage with the elimination of water..
i. With hydroxylamine
ii. With hydrazine
iii. With phenyl hydrazine
iv. With 2,4 dintro phenyl hydrazine, Brady’s reagent
v. With semi carbazide
REACTIONS OF CARBONYLS
1. Tollen’s reagent diamminesilver(I) Ag(NH3)2, cause oxidation of
aldehydes to give silver mirror, used for detecting aldehydes. [Tollen’s
test]. When the aldehyde is mixed with Tollen’s reagent in the test tube,
Ag(s) is formed. It can be seen as a mirror in the test tube. Hence the test
is called ‘silver mirror’ test for aldehydes.
+ - - -
CH3CHO + 2Ag(NH 3)2 + 3OH 2Ag + CH3COO + 4NH 3
Silver mirror
Addition of ammonia to AgNO3(aq) converts the silver ions to
diamminesilver(I) ions [Ag(NH3)2]. The solution is also called ammoniacal
silver nitrate (Tollen’s reagent). Aldehydes are good reducing agents, hence
they are easily oxidized to acids as seen above.
KETONES ARE HARD TO OXIDIZE
2. REACTION WITH PHENYLHYDRAZINE
This is useful in the identification of the aldehyde or ketone. The
compound, 2,4-dinitrophenylhydrazine, is orange in colour, and will
react with aldehyde or ketone to give orange-yellow colour/ solid, called
2,4-dinitrophenylhydrazone. The result can be used to characterize and
identify the C=O.
H +
_ H H
+ H2N NHC 6H5 + H 2O
O NNHC 6H5
Benzaldehyde phenylhydrazine
Benzaldehyde phenylhydrazone
3. Reaction with Fehling solution
Aldehydes are capable of reducing Cu2+ to Cu+. Alkaline solution of
copper(II) tartrate referred to as ‘Fehling’s solution’ is a clear royal
blue solution. If warmed with aldehyde, there forms orange-yellow
ppt of copper(I)oxide.
4. Haloform Reaction (Iodoform test)
Though ketones are difficult to oxidize, the iodoform test is one
oxidation reaction of ketones that is useful. The test is actually for
identifying methyl carbonyls [CH3C=O].
It is given by methyl ketones like propanone and butanone. Likewise
ethanal and ethanoyl moieties will behave positively with this test.
Solution of iodine in NaOH(aq) is warmed with propanone. The solution
has iodate(I) ion ‘IO-’, which act as the oxidizing agent. Yellow
precipitate of triiodomethane [iodoform] is seen.
CH3COCH3(aq) + 3 IO-(aq) CH3COO-(aq) + CHI3 (s) + 2OH-(aq)
Yellow ppt
5. Reduction of carbonyls to methylene
CH2CH2CH3
O ngCl
CCH 2CH3 Clemmensen reduction
H2NNH2, HO-, CH2CH2CH3
Wolff-Kishner reduction
• Above are two of other effective methods for reducing a ketone
carbonyl to a methylene group.
• Clemmensen reduction uses an acidic solution of zinc dissolved in
mercury as the reducing reagent.
• Wolff-Kishner reduction employs hydrazine [recall we used above-
H2NNH2] under basic conditions.
