CHE 176

(Dr S.A. Aboaba)

1
Outline
• Carboxylic acids
• Derivatives of carboxylic acids(esters, acid
halides, acid anhydrides, amides)
• Carbohydrates
• Cellulose, starch and glycogen
• Proteins and amino acids
• Synthetic polymers
• Soaps and detergents.
2
CARBOXYLIC ACIDS
Carboxylic acids possess –COOH functional
group [ C O ]. Simply carboxyl group.
OH
The carboxyl group is a combination of carbonyl
and hydroxyl group.
O O
C = +OH
OH C
Carboxyl grp Carbonyl Hydroxyl
grp grp
The presence of the carboxyl group in carboxylic
acids differentiate them structurally from mineral
acids. E.g of mineral acids areHCl,H2S O4,etc.

3
CLASSIFICATION OF CARBOXYLIC ACIDS
• Carboxylic acids are classified based on the
number of carboxyl groups per molecule.
• One carboxyl – mono-carboxylic acid
• Two carboxyl – di-carboxylic acid
• Three carboxyl – tri-carboxylic acid.
• Ethanoic acid, oxalic acid and citric acid are
e.gs of mono, di, and tri-carboxylic acids
respectively(Draw the structures of these acids)
• General formula CnH2n+1COOH
4
NOMENCLATURE
From alkane, delete the –ane and add –oic
Alkanoic acid
Examples: IUPAC Common name
HCOOH Methanoic acid Formic acid
O
CH3C
OH Ethanoic acid Acetic acid
O
CH3CH2C
OH
Propanoic acid Propionic acid
O
CH3CH2CH2C Butanoic acid Butyric acid
OH
5
Cl Cl O
H C C C
H H OH

2,3-Dichloropropanoic acid
•Note: The carbon atom in the carboxylic acid
functional group is always numbered 1.

6
PROPERTIES
•Carboxylic acids form H-bond with water or any
other polar solvent.
•The lower molecular weight acid show
appreciable water solubility but this decreases
as the molecular weight of the acid increases,
i.e as the length of the hydrocarbon chain
increases.
CO 2H

is not soluble in cold water but soluble in

hot water.
•CO2H have sharp, pungent odour
7
•The lower members are liquid at room
temperature i.e those with less C - atom. It is
known that anhydrous ethanoic acid freezes to
an ice like solid below 17oC and therefore gives
it its name as glacial acetic acid.
•C1-C3 are colourless pungent-smelling liquids
•C4-C9 are colourless oils.
•C10 and above are colourless solids.
•Carboxylic acids are more acidic than phenols
and alcohols.
•Those that are liquid have higher boiling
point than alcohol.
8
•The high boiling point is due to the association
in the liquid and solid state of COOH and this is
due to intra-molecular bonding.
O H O
R C C R
O H O
•They are more acidic than alcohols because the
polarity of O-H bond is further enhanced by the
electron withdrawing action of the carbonyl
group thereby making its O-H bond more polar
than what is observed in alcohols.
9
PREPARATION OF CARBOXYLIC ACIDS
1. Oxidation of a primary (1o) alcohol
-
(
i
)
K
M
nO
/
O
H
4
RC
OH
2RH
2
(ii)
O
2
[O]
CH3CH2OH CH3CO2H
2. Oxidation of aldehyde
KMnO4
RCHO or K2Cr2O7
RCO2H
[O
CH
C
3C
C
H
3
2
3. Hydrolysis of ester:
(i) If the hydrolysis is in alkaline medium, it is
termed Saponification.
10
Generally:
RCO2R' + NaOH RCO2-Na+ + R'OH

H+

RCO2H
(a)
O O
NaOH, H2O
CH3C CH3CH2OH + CH3C

OCH2CH3 O-Na+
dil. HCl

O
CH3C + NaCl
OH
(b)
CH3-CHCO2CH2CH3 (i) NaOH/H2O CH3-CHCO2H + CH3CH2OH
(ii) dil. HCl
CH3 CH3
ethyl-2-methyl propanoate 2-methyl propanoic acid

11
(ii) Acid hydrolysis of esters can also give
carboxylic acids.

+ H2O H+
RCO2R' RCO2H + R'OH
+
H
3
2
2
5
+
CH
CO
C
HH
O
2C
C
3H
+
C
2H
O
25

4. Oxidation of Alkybenzenes
R
KMnO + COOH
4/H

heat

12
DERIVATIVES OF CARBOXYLIC ACID
* There are four types of carboxylic acid derivatives:
acyl halides, acid anhydrides, acid amides and esters.
O
* The general form of these derivatives is R C
X
where X is more electronegative than carbon.

X could be OR = Esters

Cl-, Br-, I- = Acid halides

O
when X = OC = An acid anhydride
R'
(if R ≠ R then we have a mix anhydride)
I

13
R1 O
Amide i.e Alkanamie, e.g.
X = N CH3CH2CNH2
R2 propanamide

14
• Derivatives of carboxylic acid undergo nucleophilic
substitution reaction.
• The carboxylic carbon atom have δ+ and act as a
nucleophilic site.
O O
-
R +
CN
u R
CX
+
X Nu
• The power of the δ+ depends on the electron donating
or withdrawing power of X.
• High δ+ means a high nucleophilic substitution
reaction rate.
• Acylchloride>acid anhydride>carboxylic
acid>ester>amides
15
• Derivatives of carboxylic acid undergo nucleophilic
substitution reaction.
• The carboxylic carbon atom have δ+ and act as a
nucleophilic site.
O O
-
R +
CN
u R
CX
+
X Nu
• The power of the δ+ depends on the electron donating
or withdrawing power of X.
• High δ+ means a high nucleophilic substitution
reaction rate.
• Acylchloride>acid anhydride>carboxylic
acid>ester>amides
16
ESTERS
•Esters are sweet smelling products.
•Many natural scents and the flavours of many fruits are
partly due to traces of esters.
•The saturated ones are colourless.
•Esters are prepared from acids and alcohols.
•The general formula is;
O

R C OR'

where R and R’ can be the same or different alkyl

groups.
* The bridging oxygen atom has two lone pairs of electron in
its p orbital which can interact with the orbital of the C=O,
the c-atom of the ester linkage is therefore slightly +ve and
susceptible to nucleophilic attack.
17
• They are mostly used as solvents e.g in the industry
as solvents for oils, resins, gums, varnishes and
paints.
•The name of an ester is made up of two words in
form of ‘alkyl alkanoate’.
• ‘Alkyl’ derived from the original alcohol and
‘alkanoate’ from the original carboxylic acid.

O O
H 3C C -O H + H O C H 3 H 3C C -O C H 3
a c id a lc o h o l m e th y le th a n o a te
(e th a n o ic a c id ) (m e th a n o l)

18
NOMENCLATURE OF ESTERS
Look for the –OCH3 (side) part (i.e. oxygen side)
and note the number of C-atoms there (this is the
alcohol part), then note the side that has
carbonyl (the acid part).
• Parent name comes from acid
• Alkyl name comes from alcohol

e.g. O O
H C OCH3 H3C C OCH2CH2CH3
Methyl methanoate Propyl ethanoate

19
PREPARATION OF ESTERS
(i) ACID + ALKANOL ESTERS
O O
+ CH CH OH HCl
H 3C C OH 3 2 H3C C OCH 2CH 3
Ethanoic acid Ethanol Ethyl ethanoate

1o alcohols are the easiest, others are not because

of steric hindrance.
(ii) Acid halides + Alcohols Esters
e.g. O O
CH3CH2C + CH3OH H3CH2C C
Cl OCH3

20
(iii) Acid anhydride: Nucleophilic attack

O O O O

R C O + R' OH O C R
C R R C

O
A lc o h o l
A n h y d r id e
R H

O
O O
O
OCR
+ R
C
R C O R' R COH
O
E
s
te
r R'
H

21
ACYL HALIDES
•Prepared from acids using SOCl2, PCl5, PBr3, PCl3.

(i) 3 C H 3 C O O H + P C l3 3C H 3C O C l + H 3P O 3
COOH COCl

(ii)
+ P C l5 + P O C l3 + H C l

O O
( iii) CH 3 C + SOC l 2 CH 3 C + HCl + SO 2
OH Cl

22
ACID ANHYDRIDES
•The simplest method of preparing acid anhydrideis
the reaction of two carboxylic acid molecules in the
presence of phosphorous pentaoxide (P2O5).
•This yields 1 molecule of acid anhydride and
water.
•This is an example of condensation reaction.
O
R C
P2O5
2 RCOOH O + H2O
R C
O
Acid anhyride

23
• Industrially, ethanoic anhydride is prepared by
passing ethenone (ketene), a gas into ethanoic acid.

H
C
=
C
=
O
+
2C
H
C
O
O
3C
HC
33
• (ethenone) (ethanoic acid) (ethanoic anhydride)

O O O O

CH3C CCH3 CH3C CCH2CH3

O O
Ethanoic acid anhydride
Ethanoic propanoic anhydride
acetic anhydride

24
AMIDES
•The name of the related acid is used first and the
–oic of the acid is replaced with amide especially
for 1o amide. E.g Ethanamide (instead of ethanoic
acid).
• 2o and 3o amides have alkyl at the beginning of
the name e.g. N-ethyl butanamide and N,N-
dimethyl methanamide.

O
CH3C NH2 1oamide(2Hydrogen)
Ethanamide

25
O
o
CH3C NHCH3 2 amide (1 Hydrogen)
N-methyl ethanamide
O
N(CH
) o
CH
3C 32 3ami
de(
NoH
y
dr
oge
n
)
N
,
N-d
i
m e
t
hyle
t
han
am
i
de
O
H3CH2C C N(CH3)2 3o amide (No Hydrogen)
N,N-Dimethyl propanamide
Note:Cyclic amides are called LACTAMS
26
PREPARATION OF AMIDES
(1) Ammonolysis: Esters, acid chlorides and acid anhydrides
are treated with conc. Ammonia to form amides.
1
a. R C O O R + N H 3 R C O N H 2 + R 1O H

b . R C O C l + 2N H 3
R C O N H 2 + N H 4C l

- +
C . (R C O )2O + 2N H 3 R C O N H 2 + R C O 2 N H 4

(2) Dehydration of ammonium salts: When ammonium salts

or carboxylic acids are slowly distilled, water is removed
and amides are obtained.
h
e
a
t
RCOO
4 R
C
O
N
H+
H
O 22

27
O O
(1) CH3C + 2 NH3 CH3C NH2 + NH4Cl
Cl
Ethanamide
O O
CH3NH2
CH3C + 2 NH3 CH3C NHCH3
Cl
N-methyl ethanamide
(2)
From acid anhydride + NH2 Amide + Acid
CH3NH2
(3) (CH3)2NH
Acids + NH3 Δ Amide
or amine 28
REACTIONS OF ACID DERIVATIVES
Nucleophilic Reactions
•All of them undergo nucleophilic attack on the O
C
to give products.
R
2 NH
Nucleophiles: OH , N R , 3 , ROH , H2O
R3

•When the nucleophile is H2O or OH-, then reaction

is hydrolysis.
•All of them are hydrolyzed to give corresponding
COOH.
29
O O O O
CH3C O CCH3 + H2O CH3C OH + CH3C OH

•If your hydrolysis is catalyzed by mineral acid, what

is found is COOH because the medium is acidic but
when the medium is alkaline, what is formed is salt of
the carboxylic acid.

Ester + Grignard reagent 3o alcohol

O CH2CH3
+ CH3C OH
CH3C OCH3 2 CH3CH2MgBr CH2CH3
•Remember that grignard reaction with methanal gives 1 o
alcohol.
30
❖Reduction
•All acid derivatives on reduction gives 1o alcohol
and the reducing agent is LiAlH4.
CH 3 CH 3
CH 3 CHCH 2 CO 2 H CH 3 CHCH 2 CH 2 OH

LiAlH 4
CH 3
CH 3 CHCH 2 CO 2 CH 3

•For other acid halides which are strong, NaBH4

will reduce them but not esters which are weaker.
31
AMINES (-NH2 GROUP)
•Amines contain nitrogen but the N atom is linked
to ordinary C-atom which may be sp3, sp2, and in
very rare cases sp hybridized.
R2
•They have the structure R N 3 & are
nucleophiles. R
• Since the carbons are not pulling the electrons
more powerfully, they are basic and more than
alcohol.
•Especially the N is less electronegative than O,
therefore the lone pair electron is less strongly
held in amines than in alcohol, ether.
•General formula: CnH2n+2+xNx
32
•From alkane, remove the (-e) at the suffix and
replace by amine Alkanamine
CH3NH2 – Methanamine
•1o amine are represented by the general formula
R-NH2 where R can be an alkyl or aryl group.
•The name of a 1o amine is made up of the number
of carbon skeleton from the corresponding alkane
or benzene and also the suffix ‘amine’.
NH2
e.g. CH3NH2
Methylamine
phenylamine
33
➢2o amines are represented by the general formula
R N H in which R and R’ can be alkyl or aryl group.
R'
e.g. H3C N H H3C N H
H3C N H CH2CH3
CH3 N-methylethylamine
Dimethylamine N-methylphenylamine
➢3o amines are represented by the general formula
R N R" where R, R’, R” can each be an alkyl or an
R' aryl group.
CH3
e.g. H3C N CH3 N
CH3
Triethylamine N-Methyldiphenylamine 34
Physical Properties
•They are polar substances, they are not as volatile
as alcohol.
•Their solubility in water is due to their polarity.
•The longest molecule is more soluble than their
corresponding alcohol because the hydrogen
bonding in water using the N is stronger in amines
than using the oxygen in alcohols.
•Amine with few C-atoms are gases and have a
characteristic ‘ammonia’ odour while the higher
ones are liquid with a distinctive ‘fishy’ odour.

35
3. Reduction of nitro compounds
RNO2 reduction RNH2
ArNO2 reduction ArNH2

Reducing agents
•H2/Catalyst (e.g Pt, Ra-Ni, Pd)
•Metal (Sn,Zn)/HCl

36
- R
RNH2 + R'X OH
NH + HX
R'
2o amine

R
R
N R'' + R'"X R' N R"' X-
R' R"
Quaternary ammonium salt

37
REACTIONS OF AMINES
(1) Amines form salt with acids
RNH2 + HX RNH3+ + X-
(2) Reaction with HNO2 (Nitrous acid):
This reaction is used to differentiate amines.
(a)i. For 1o amines
HCl + NaNO2 + CH3CH2OH
CH3CH2NH2 N2
0OC effervescence + CH2=CH2
ii. For 1o aromatic amines
NH2 HCl +NaNO2 N2+Cl- alkaline Azodyes
0OC phenol (red, blue, e.t.c)
diazoniumsalt
38
(b) 2o Amines
H3C N H + HCl + NaNO2 H3C NNO + H2O
CH3 CH3
Nitroso compounds
yellow oil
(NITROSO AMINE)
(N-nitrosodimethylamine)

(c) 3o Amines + HNO2 NO REACTION

39
CHE 177 2014/15 STUDY QUESTIONS I
1. Name the following compounds:
• CH3CH(OH)COOH
• (CH3)3C.COOH
• PhCH2COOH
• (CH3)2CHCOOH
2. Draw the structure of the following:
• Octadecanoic acid
• 2-chloroethanoic acid
• Ethanoylchloride
• 2-hydroxybenzoic
3. Write the equation involving sodium hydroxide and
• 2-methylpropanoic acid
• Oxalic acid
• ethanoic acid
4. List properties of carboxylic acids and all its derivatives.

40
5. Esters, acyl halides, anhydrides and amides have electron deficient carbonyl
atoms, arrange these classes of compounds in the order of (i) increasing electron-
deficiency of their carbonyl carbon atoms. (ii) increasing rapidity of reaction with
a nucleophile.
6. Complete the following reactions:
• CH3COCl + NH3 ?
• CH3COOR + NH3 ?
• (CH3CO)2 + NH3 ?
7. Name the following naturally occurring carboxylic acids (fatty acids);
• CH3(CH2)10COOH, CH3(CH2)12COOH, CH3(CH2)14COOH, CH3(CH2)16COOH.
8. Draw the structure of the following compounds;
• 1-methylethylpropanoate
• Phenyl propanoate
• N-N-dimethyl propanamide
• Ethyl-2-methyl propanoate
• N-ethyl-N-methyl propanamide

41
CARBOHYDRATES
•They are compounds containing C, H and O and
have the general formula CnH2nOn.
•The simplest form of carbohydrate is glucose
where n = 6 i.e C6H12O6.
•Glucose has the formula below; and also exist in
the cyclic form. CHO
HC OH
HC OH
HC OH
HC OH
H2C OH 42
•Carbohydrates are either polyhydroxy aldehydes
or ketones, or compounds that that yield
polyhydroxyaldehydes or ketones on hydrolysis.
•Simple carbohydrates are synthesized mainly by
chlorophyll containing plants through a process
called photosynthesis. This involves CO2 from air
and water from the soil to combine to form simple
CH2O (mainly glucose) and oxygen.

light
6CO +
2(g) 6H O
2 (l)chlorophyl C6H12O6(s)+6O2(g)
glucose
43
•Glucose is an example of polyhydroxyaldehyde
because it contains the aldehyde functional
group.
•While fructose is an example of
polyhydroxyketone with a ketone functional
group.
C H 2O H
C O
HC OH
fructose
HC OH
HC OH
C H 2O H 44
Assignment
– Draw the following forms of α,β-glucose:
• Open chain
• Fischer Projection
• Harworth projection
• Chair conformation.

45
•Carbohydrates are classified into three (3)
groups
namely;
(1)Monosaccharide e.g. Glucose and fructose
with the molecular formula C6H12O6.

Classification of Monosaccharides
• They are classified according to the number
of C-atoms in one molecule. The prefix tri,
tetra, penta, hexa, indicates the number of C-
atoms, and then the term –ose ends the name
of the molecule. E.g a 6 carbon molecule is a
HEXOSE 46
• Monosaccharides can also be classified in
terms of the functional group either aldehyde
or ketone.
aldo- is added before a molecule if it contains
an aldehyde while keto is added if it is a
ketone group.
Therefore, a 6-carbon atom monosaccharide
with an aldehyde function is called
ALDOHEXOSE.
6-carbon atom with a keto group is KETOHEXOSE

47
• Stereochemistry of Monosaccharide
The use of D & L system is often used in
carbohydrate chemistry. But the most
naturally occurring carboyhdrate have the
D-configuration.
D = Dextro, L = Laevo
(Dextro and Laevo rotatory about the plane of
polarised light.
(What do you understand by Chirality? Use
glucose and fructose as examples)
48
(2)Disaccharide e.g. Sucrose, Maltose, Cellobiose
with molecular formular C12H22O11.
➢ This second group of carbohydrates can be
hydrolyzed to produce monosaccharides. For
example;
• Sucrose hydrolysis Glucose and fructose
(Table sugar)

• Maltose hydrolysis 2 molecules of Glucose

• Cellobiose hydrolysis 2 molecules of Glucose

49
(3) Polysaccharides e.g. Starch & Cellulose have
the molecular formula (C6H12O6)n. These contain
several molecules of glucose in their structures
(more than 1000 units).

❖Common disaccharides as mentioned above is

made up of glucose molecules or fructose
molecules with the elimination of water molecule.
❖The bond formed between two monosaccharides
is called a GLYCOSIDIC LINKAGE.

50
E. g. Maltose
CH2OH CH2OH
O O
H H H H H H
OH OH H OH OH OH H OH
H OH LOST
H OH -H2O
 glucose  glucose
CH2OH CH2OH
O O
H H H H H H
OH OH H O OH H OH
H OH H OH
glycosidic
linkage

51
CELLULOSE
•Cellulose is common in nature especially in
plant cell walls, in fibres and some enzymes.
•Cellulose is a linear polysaccharide with many
glucose unit.
•The glycosidic linkage is beta (β) and the
position is 1 to 4 linkage.

52
STARCH
•Starch and cellulose are more or less similar.
•The only difference is their linkage.
•While cellulose is β, starch is α.
•There are different kinds of starch. The amylose
and amylopectin.
•When starch is heated up in water, the granules
swell up and produces amylose and amylopectin.
•Amylose consists of glucose units linked together
through α-1,4 linkage.
•Amylopectin is linked with α-1,4 and -1,6 and
this makes the structure of amylopectin
53
branched.
GLYCOGEN
•Glycogen is another form of polysaccharide.

• It is used by animals for storing glucose for

further use.

•Glycogen is more or less like amylopectin

structurally because it has α-1,4 and -1,6
linkage.

54
USES OF CELLULOSE AND STARCH
(1) Cellulose are used as fibre
(2)The acetate of cellulose are used as xanthate
ester which is also used for film and in filament
production.
(3) They are also used in rayon manufacture.
(4) Starch are used as binder in drug industry.
(5) Production of alcohols.
(6) As finishers in furniture industries.

55
SYNTHETIC POLYMERS
•A compound which consist of a very large number
of a particular repeating unit linked together in
the same molecule is called a POLYMER.
• Materials we use in our day to day activities are
made up of synthetic polymers, e . g shoe sole
clothing, plastics, photographic films etc.

•There 2 major classes of polymers;

(1)Addition or chain-growth polymer.
E.g polyethylene - bottles, bags.
Polyvinylchloride (PVC) - pipes, vinyl plastics.
56
• Polystyrene – foam insulation, plastics
• Poly acrylonitrile – blankets, stimulated fur
(2). Condensation or Step-growth polymer:
Examples are:
• Nylon – a polyamide used in fibres, clothing.
• Dacron – a polyester used in clothing and is
responsible for the wrinkled behaviour of
many fibres.
• Polyurethane spandex – foams, coatings.

57
USES
•Used for packing food, making of soap cases,
small bowls, toys and unbreakable goods.
•Because they are resistant to the actions of
acids, alkalis and most chemicals, they are often
used for lining the inside of industrial chemical
plant and for bottles for storing many chemicals
in the laboratory.

58
SOAPS AND DETERGENTS
•Saponification or alkaline hydrolysis of
triacylglyceride produces glycerol and a mixture
of salt of long chain carboxylic acid.
•This salt of long chain carboxylic acid is called
SOAP.
•Saponification is the common way in which most
soaps are manufactured.
•Fat and oils are boiled in aqueous NaOH until
hydrolysis is complete.
•Addition of NaCl to the mixture causes the salt to
precipitate (as sodium carboxylate precipitate)
59
•The salts are usually purified by several
precipitation processes.
CH2OCOR1 CH2OH
H2O
CHOCOR2 + 3 NaOH CHOH + 3 RCOO-Na+
Sodium carboxylate
CH2OCOR3 CH2OH (SOAP)
Triglyceride glycerol

•The smooth soap that precipitates is dried,

perfumed and pressed into bath or household use.
•Dyes are added to make coloured soaps:
antiseptics are added for medicated soap.
•Sand and Na2CO3 as well as other fillers can be
added to make scouring soap.
60
•Soaps are almost completely miscible with water.

•Soaps act as cleansers because the two ends of a

soap molecule are so different.

•The sodium ends of the long chain molecule is

ionic and therefore hydrophilic (water loving). It
tries to dissolve in water.

•The hydrocarbon portion of the molecule however

is non-polar and therefore lipophylic (fat loving).

•The net effect of these two opposing tendency is

that soaps are attracted to both grease and water. 61
• Once the surface of the grease droplet is covered by
many soap molecules, a micelle can form with a tiny
grease droplet at its centre.
• This grease droplet is easily suspended in water
because it is covered by the hydrophilic carboxylate
groups of the soap.
• The resulting mixture of two insoluble phases
(grease and water) with one phase dispersed
throughout the other in small droplets, is called
am EMULSION, we then say the grease has
been emulsified by the soap solution.
• When the wash water is rinsed away, the grease
goes with it.
62
•The usefulness of soaps is limited by their
tendency to precipitate out of solution in hard
water.
•Hard water is water that is acidic or that contains
ions of Ca, Mg, or Fe.
•Soap precipitates in hard water because of the
chemical properties of carboxylic acid group.

63
SYNTHETIC DETERGENTS
• Synthetic detergents avoid precipitation by using
other functional groups in place of carboxylic salt.

• Sodium salt of sulphonic acids are the most widely

used class of synthetic detergents.

• Sulphonic acids are more acidic than carboxylic

acids, so their salts are not protonated, even in
strongly acidic wash water.

• Ca, Mg, or Fe salts of sulphonic acids are soluble

in water, so sulphonate salts can be used in hard
water without forming a scum (i.e foam). 64
O H+
R S O- Na+ + Ca2+ NO
O Mg2+ PRECIPITATE
An alkylbenzene Fe3+
solfonate detergent

65