CHE 176 ORGANIC CHEMISTRY 1

BY
DR DORCAS O. MORONKOLA,
CHEMISTRY DEPARTMENT,
UNIVERSITY OF IBADAN, IBADAN.
NIGERIA.
CHE 176 Course Content
Basic concept of organic chemistry: definition and importance of organic chemistry: atoms,
atomic and molecular orbitals including bonding. Unique nature of carbon, Hybridization.
Determination of molecular composition and structure of organic compounds. Functional
group classes of organic compounds. Nomenclature of organic compounds. Reaction
mechanism and Kinetics. Types of organic reactions. Factors affecting organic reactions.
Synthesis reactions and uses of alkanes including petroleum, alkenes, alkynes, benzene and
aromatic compounds; halo alkanes and alkanols.
Alkoxyalkanes, alkanamines, carbonyl compounds (alkanals and alkanones), carboxylic acids
and derivatives.
Brief introduction to bio-molecules: carbohydrates and proteins; Synthetic polymers.
Introduction to spectroscopy: Infra-red, UV, NMR and Mass Spectroscopy. Basic Concept of
organic synthesis.
CHE 176 Course Content / Lecturers
Prof. O.O. Sonibare:
Basic concept of organic chemistry: definition and importance of organic chemistry: atoms,
atomic and molecular orbitals including bonding. Unique nature of carbon, Hybridization.
Determination of molecular composition and structure of organic compounds. Functional
group classes of organic compounds. Nomenclature of organic compounds. Reaction
mechanism and Kinetics. Types of organic reactions. Factors affecting organic reactions.
Dr Ganiyat K. Oloyede:
Synthesis reactions and uses of alkanes including petroleum, alkenes, alkynes, benzene and
aromatic compounds; halo alkanes and alkanols.
Dr Dorcas O. Moronkola:
Alkoxyalkanes, alkanamines, carbonyl compounds (alkanals and alkanones), carboxylic
acids and derivatives.
Dr Sherifat A. Aboaba:
Brief introduction to bio-molecules: carbohydrates and proteins; Synthetic polymers.
Introduction to spectroscopy: Infra-red, UV, NMR and Mass Spectroscopy. Basic Concept of
organic synthesis.
CHE 176: ORGANIC CHEMISTRY 1
Dr Dorcas O. Moronkola:
Alkoxyalkanes (Ethers), Alkanamines
(Amines), Carbonyl compounds (alkanals
and alkanones i.e. Aldehydes and Ketones
respectively), Carboxylic acids and
derivatives.
[NB: Nomenclatures and Chemistry with
Mechanisms of Reactions, Preparations /
Synthesis and Uses of the Compounds
Discussed in all cases].
CHE 176 ORGANIC CHEMISTRY 1
BY
DR DORCAS O. MORONKOLA,
CHEMISTRY DEPARTMENT,
UNIVERSITY OF IBADAN, IBADAN.
NIGERIA.
CHE 176 Course Content
Basic concept of organic chemistry: definition and importance of organic chemistry: atoms,
atomic and molecular orbitals including bonding. Unique nature of carbon, Hybridization.
Determination of molecular composition and structure of organic compounds. Functional
group classes of organic compounds. Nomenclature of organic compounds. Reaction
mechanism and Kinetics. Types of organic reactions. Factors affecting organic reactions.
Synthesis reactions and uses of alkanes including petroleum, alkenes, alkynes, benzene and
aromatic compounds; halo alkanes and alkanols.
Alkoxyalkanes, alkanamines, carbonyl compounds (alkanals and alkanones), carboxylic acids
and derivatives.
Brief introduction to bio-molecules: carbohydrates and proteins; Synthetic polymers.
Introduction to spectroscopy: Infra-red, UV, NMR and Mass Spectroscopy. Basic Concept of
organic synthesis.
CHE 176 Course Content / Lecturers
Prof. O.O. Sonibare:
Basic concept of organic chemistry: definition and importance of organic chemistry: atoms,
atomic and molecular orbitals including bonding. Unique nature of carbon, Hybridization.
Determination of molecular composition and structure of organic compounds. Functional
group classes of organic compounds. Nomenclature of organic compounds. Reaction
mechanism and Kinetics. Types of organic reactions. Factors affecting organic reactions.
Dr Ganiyat K. Oloyede:
Synthesis reactions and uses of alkanes including petroleum, alkenes, alkynes, benzene and
aromatic compounds; halo alkanes and alkanols.
Dr Dorcas O. Moronkola:
Alkoxyalkanes, alkanamines, carbonyl compounds (alkanals and alkanones), carboxylic
acids and derivatives.
Dr Sherifat A. Aboaba:
Brief introduction to bio-molecules: carbohydrates and proteins; Synthetic polymers.
Introduction to spectroscopy: Infra-red, UV, NMR and Mass Spectroscopy. Basic Concept of
organic synthesis.
 1
Dr Dorcas O. Moronkola:
Alkoxyalkanes (Ethers), Alkanamines
(Amines), Carbonyl compounds (alkanals
and alkanones i.e. Aldehydes and Ketones
respectively), Carboxylic acids and
derivatives.
[NB: Nomenclatures and Chemistry with
Mechanisms of Reactions, Preparations /
Synthesis and Uses of the Compounds
Discussed in all cases].
 1
• Alkoxyalkanes,
• Alkanamines,
• Carbonyl compounds (alkanals and
alkanones),
• Carboxylic acids and derivatives
(Derivatives of mono- carboxylic acids:
Acyl chlorides, Anhydrides, Esters and
Amides)
• [NB:Chemistry with Mechanisms of
Reactions and Uses of Compounds
Discussed in all cases]. [? Spectroscopic
information on each]
Recall:
• Catenation in Carbon
• Functional Groups [Structures and
Names]; Homologous series
• Alcohols
• Aromatic Compounds [e.g. benzene];
• Mono Substituted benzene compounds.
• Differences between Phenyl and Benzyl
groups.
CATENATION
• Recall: Organic compounds contain carbon
and essentially H. Usually carbon in organic
compounds are bonded to Hydrogen atom
(with valency 1) to form single covalent
bonds
• Sometimes carbon atoms form continuous
and multiple bonds with itself and other
hetero-atoms [e.g. O, N, S, X]. Carbon can
also form cyclic and aromatic compounds
• This ability of carbon to form enormous/
divers types and great number of
compounds is known as CATENATION.
 XPhenyl group [Aryl group]: Benzyl group:

A
A

[Benzene ring act as a substituent] [Benzene with a methylene group]

OH OH
Alkyl group:
-Is an alkane minus one H atom
- They are named like their
corresponding alkane but end
with ‘yl’
- Denoted by –R
- Recall: Aryl group –Ar / C6H5-
 NB: Outline of Discussion in
Each Case
General Introduction
Identification and naming
[Nomenclature] [IUPAC/
Systematic names]
Uses, Importance and
Applications
Properties and Reactions
Preparation and Syntheses
 General Introduction:
• Alcohols, phenols and ethers are seen as organic
derivatives of water [H-O-H], where the H-atom(s) of
water is/ are substituted by hydrocarbons (alkyl/ aryl).
• When an alkyl group is substituted for a H in water, it gives
an alcohol [R-OH].
• If an aryl substitution for a H atom in water, it yields
phenol [Ph-OH].
• When both H-atoms in water are substituted by alkyl or
aryl substituents it results into ether [R-O-R/ Ph-O-R/ Ph-
O-Ph] i.e. In ethers both H atoms of water are replaced by
hydrocarbon/ organic groups.
General Introduction Contd: Examples
CH3-O-H OH CH3-O-CH3 ether
alcohol
Phenol

CH3-NH2; (CH3)2-NH; (CH3)3-N AMINES / ALKANAMINES

Carbonyl compounds: Alkanals, Alkanones, -
Carboxylic acids (RCOOH) and derivatives O
(Derivatives of mono- carboxylic acids: Acyl
+
chlorides, Anhydrides, Esters and Amides) C
R R
 Nomenclature in Ethers:
o Ethers as a class of organic compounds are simple to name. Note
the following four methods of naming ethers
1. Common names of the two groups bonded to oxygen in ether are
named in either alphabetical order, followed by/ ending it with the
word ‘ether’. These occur mostly when you have different organic
radicals bonded to the oxygen in ether, i.e. they are unsymmetrical.
Examples: CH3-O-C2H5 is ethyl methyl ether; C6H5 -O-C3H7 is phenyl
propyl ether [NB: arranged in alphabetical order]
H/W: Give names of following mixed and simple ethers: (i) C3H7-
O-C2H5; (ii) C2H5CH2-O-C4H9; (iii) C6H5-O-C2H5; (iv ) CH3-O-C6H5;
(v) C5H11-O-C3H7.
Answers: (i) Ethyl propyl ether; (ii) butyl propyl ether; (iii) ethyl phenyl
ether; (iv) methyl phenyl ether; (v) pentyl propyl ether.
2. For symmetrical ethers: When the
alkyl/aryl groups [organic radical]
bonded to the oxygen of the ether are the
same, it is a symmetrical ether, and they
are usually simple. The hyphen ‘di-‘ is
utilized. Examples: CH3-O-CH3 is
dimethyl ether; C3H7-O-C3H7 is dipropyl
ether.
H/W: Give the structures of (i) diethyl
ether (ii) dipropyl ether (iii) diphenyl
ether (iv) dibenzyl ether
 3. IUPAC name: Since ethers are alkoxy/
phenoxy derivatives of alkanes or aryl
nucleus [O-R/ O-Ph], name the smaller
R/ Ph-groups in the ether, ending in –
oxy. Usually the bigger alkyl group is the
parent e.g. CH3-O-CH3 is methoxy
methane; C2H5-O-C4H9 is ethoxy butane/
not butoxy ethane.
H/W: Give structures of following:
(i) ethoxy ethane (ii) methoxy ethane
(iii) ethoxy benzene (iv) 3-ethoxyhexane.
H/W: (a) Give the name of
following: (i) C2H5O-CH(C2H5)2
(b) Give the structures of
following: (i) [3-ethoxypentane]
(ii) 3-ethoxyhexane
H/W: Give structures of following: (i) ethoxy
ethane (ii) methoxy ethane (iii) ethoxy benzene
(iv) 3-ethoxyhexane.

H/W: Give names of following: (i) C2H5O-

CH(C2H5)2 [3-ethoxypentane]; (ii) C3H7-O-C3H7
(iii) C2H5-O-C4H9 [see earlier slides]
4. Trivial/ Common names of some
ethers are still accepted and used e.g.
Anisole for methoxy benzene; Phenetole
for ethoxy benzene. [Give its structures].
Epoxides are 3-membered cyclic ethers,
known as epoxyethane [ethylene oxide];
TetraHydroFuran [THF]

OCH3 OC 2H5
O
O

anisole Phenetole
Amines (Alkanamines)
• They are aliphatic amines
• Amines are organic compounds containing central nitrogen atom (N)
bonded to one or more C-atoms, which could be alkyl, cyclic or
phenyl (aromatic) group. See them as derivatives of ammonia (NH3),
where carbon atoms replace either one or two or the three hydrogen
atoms.
• Examples: CH3-NH2; (CH3)2-NH; (CH3)3-N
C/W:
• Try to name above as methylamine CH3-NH2; dimethylamine (CH3)2-
NH and trimethylamine (CH3)3-N
• i.e. In methylamine (a methyl group replace one-H in ammonia NH3);
In dimethylamine (2 methyl groups bond to the N); and In
trimethylamine (3 methyl groups replace all-H in ammonia NH3).
Classification of Amines:
• Depending on how many alkyl groups are bonded to the
N, the amine could be ‘primary (10), secondary (20) or
tertiary (30)’
• In primary amine one alkyl group is bonded to the N,
while in secondary amines two alkyl groups are bonded
to the N, and tertiary amines have three alkyls bonded
to the N.
• Generally primary amine (10) are R-NH2; secondary
amines (20) are R2NH and tertiary amines (30) are R3N.
[NB: the R could be same or different]
Common Names of amines:
• In addition to general rules of naming organic
compounds note the following (a) Alkyl groups bonded
to N-atom are listed in alphabetical order followed by
the suffix ‘amine’; (b) Prefixes such as di-, tri- are use,
which indicate two or three identical substituents are
bonded to the N in the amine.
• The following amine is better referred to as
(CH3)-NH-(CH2CH3) = [Ethylmethylamine];
(CH3)N(C3H7)(CH2CH3) = [Ethylmethylpropylamine];
• [NB: entire name is written as a word unlike separations
observed in alkyl halides, alkanols and alkoxyalkanes].
• C/W: Identify the class of the above amines
Systematic Names of Amines:
• The IUPAC system utilize suffix ‘amine’ to denote the
functional group (FG), where the ‘e’ ending the name of
the parent hydrocarbon is replaced by ‘amine’
• A number now identifies the carbon where N is
bonded. That number appears before the name of the
parent hydrocarbon or before ‘amine’.
• The name of other alkyl group bonded to nitrogen is
preceded by an ‘N’ written in italics, indicating that the
group is bonded to N, and not C.
CH3CH2-NH2 (ethanamine);
CH3CH2CH2CH2-NH2 (1-butanamine);
CH3CH2CH2NHCH3 (N-methyl-1-
propanamine);
CH3CH2CH2N(CH3)CH2CH3 N-ethyl-N-
methyl-1-propanamine;

C/W: Identify the class of each of the

above amines
IUPAC System of naming Amines contd.
• For all substituents in the molecule either on N or on parent
hydrocarbon, they are listed in alphabetical order with a number or
an ‘N’ preceding each. Numbering of the chain is such that gives the
FG suffix the lowest number.
• CH3CH(Cl)CH2CH2-NH-CH3 3-chloro-N-methyl-1-butanamine;
Quaternary Ammonium Salts:
• These nitrogen compounds have four alkyl groups
bonded to the nitrogen (N), hence are quaternary
ammonium salts.
• The naming is such that the alkyl groups are given in
alphabetical order followed by ‘ammonium’ all as a
word, then the counterion (accompanied anion) is
named after as a separate word.
• (CH3)4-N+ HO- Tetramethylammonium hydroxide;
(CH3CH2CH2)(CH3)2(CH2CH3)N+ Cl-
Ethyldimethylpropylammonium chloride;
 AROMATIC Amines:
• Simplest is phenylamine commonly called aniline [C6H5-
NH2]
• The other simple compounds are named as derivatives of
phenylamine
• Examples:
• Methylphenylamines are all called TOLUIDINES e.g. 2-/o-,
or 4-/p- Methylphenylamine (toluidine) [CH3-C6H5-NH2]
• N-Methylphenylamine [C6H5-NHCH3]; Diphenylamine
[C6H5-NH-C6H5];
Structures of Some Aromatic Amines:
 The Carbonyls
Aldehydes and Ketones
Aldehydes and ketones are usually
referred to as the carbonyl compounds.
There are other classes of organic
compounds with carbonyl in their
functional group. Others includes
carboxylic acids [RCOOH], esters/
alkanoates [RCOOR’], anhydrides
[RCO-O-COR’], acyls [RCO-], and
amides [-CONH-].
Aldehydes have a single H attached to the
carbonyl carbon, and are usually terminal i.e. at
one of the end positions, hence taking no 1
when numbering; but ketones have two
hydrocarbon groups bonded to the carbonyl
carbon, and are never terminal. O
O
R R'
R H Ketone
Aldehyde
ALDEHYDES:
•general formula : RCHO/ ArCHO. The
functional group is O

R H
•Aldehydes originated from the name of
the alcohol that was dehydrogenated to
obtain the aldehyde =[alcohol
dehydrogenated]. Saturated aliphatic
aldehydes are referred to as ALKANALS.
 ALDEHYDES/ ALKANALS:
.General formula : RCHO/ ArCHO. The functional group is

R H
Aldehydes originated from the name of the alcohol that
was dehydrogenated to obtain the aldehyde =[alcohol
dehydrogenated].
Saturated aliphatic aldehydes are referred to as
ALKANALS
Additional Rules for Aldehyde
Nomenclature:
In addition to the general rules following should be
considered when naming an aldehyde/ alkanal:
• Name the longest carbon chain containing the carbonyl
group by replacing the ‘e’ in alkane/ aliphatic counterpart’s
name with ‘–al’ [-aldehyde is used for trivial names].
• No number is inscribed to the carbonyl aldehyde group
when naming, because it always appear at end of the chain.
• When branching/ substituent is present, the CHO carbon
takes no.1, and ascribe lowest possible number to the
branching/ substituent. Hence ‘1’ in carbon of CHO is not
usually specified in the name of alkanals.
Additional Rules for Aldehyde Nomenclature
Contd:
•When other functional groups are present,
their positions are specified with
numbering.
•The Greek letters α, β, ψ, and δ are seldom
used. The lettering starts from the carbon
atom adjacent to the carbonyl carbon. It
implies that C-2 is α-C, C-3 is β-C, etc.
 O
H3C

H
H3C
is 2-methylpropanal / α-methylpropanal

CH3 3-chloro, 2-ethyl, 4-methyl, pent-3-enal

C2H5

H3C
CHO The aldehyde of
Cl O H benzene is called
‘benzaldehyde’,
in almond.
H/W:

Present the structures of the

following aldehydes
(i)pentanal (ii)3-chlorobutanal
(iii)2-methyl-2,butenal
(iv)phenylethanal
(v)4-methylpentanal
(vi) 4-chlorobenzaldehyde.
KETONES: with two organic radicals
[hydrocarbons] bonded to the C=O carbon

R R'
Naming of Ketones:
Generally naming of ketones in IUPAC system
involves replacing the ‘-e’ of its corresponding
alkane/ hydrocarbon by ‘-one’. When the ketone
is unbranched their common names are still
used. Example propanone [dimethyl ketone] is
also called ‘acetone’, which IUPAC still accepts.
Alkyl groups bonded to carbonyl carbon are
seldom named as substituent and are listed
alphabetically, then followed by ‘ketone’. The
following rules should be added to the general
rules of naming organic compounds: i.e.
Rules for Naming Ketones
• You name the longest carbon chain containing the carbonyl
group by replacing the ‘-e’ in the corresponding alkane/
hydrocarbon name with ‘-one’.
• Carbon should be numbered on the main chain starting
from the end nearest to the carbonyl group.
• You also write the number of the carbonyl carbon in front of
the named ketone.
• Other substituent on the carbon chain are also numbered
and named accordingly.
Practise with these:
(i)

O
O
(ii)
CH3
H3C CH3
H3C
(iii)

(iv)
H3C CH3
H3C CH3
O
Answers
• (i) Propanone
• (ii) Butanone
• (iii) 2-Pentanone
• (iv) 3-Pentanone
 H/W: Write out the IUPAC names of each of
the 3 ketones below:

1. 2. 3.
O H3C H3C
Cl Br
CH3 H3C
H3C CH3 CH3
H3C O Br H3C
H3C O Br CH3

H/W: Show the structure of

(i) phenylethanone [acetophenone]
(ii) diphenylmethanone [benzophenone]
Answers
• 1. 3-methylbutanone
• 2. 5-bromo, 2,6-dimethyl, 3-heptanone
• 3. 2-chloro, 5,6-dibromo, 4,7-dimethyl, 3-octanone
Answers
1. 3-methylbutanone [not 3-
methylbutan-2-one]
2. 5-bromo-2,6-dimethyl [3-heptanone/
heptan-3-one]
3. 2-chloro-5,6-dibromo-4,7-dimethyl-
[3-octanone/ octan-3-one]
Answer
• (C) 6-chloro, 3-hexanone
 Carboxylic acids
• Carboxylic acids are class of organic compounds that have
the carboxyl functional group (-COOH), i.e. the carbonyl
(C=O) and hydroxyl (OH) groups, hence its name.
• But the two groups modify each other, such that chemical
reactivity of the carboxyl group does not resemble either of
the two constituents as separate entity.
 Carboxylic acids Contd.
• Their saturated open chain (aliphatic) monocarboxylic acids
are called ‘Alkanoic acids’ with general formula:
CnH2n+1COOH, simply put as ‘RCOOH’
• They are also referred to as ‘fatty acids’ since most of the
higher members obtained from natural sources are
constituents of natural fats. E.g. Palmitic acid
(hexadecanoic acid), stearic acid (octadecanoic acid), oleic
acid (cis-octadec-9-enoic acid)
• Most common acid is ethanoic (acetic) acid [CH3COOH].
[Recall: Glacial acetic acid].
Nomenclature In Carboxylic acids :
• The IUPAC name makes use of the corresponding alkane
with same carbon chain, usually the longest chain with the
carboxyl FG, and replacing the ‘e’ of corresponding alkane
name with the suffix ‘-oic’. It is numbered such that carbon
of the carboxyl is no. 1.
• Other substituents are located and named on the main
chain.
 Nomenclature In Carboxylic acids
Contd:
• Positions of substitutions are given [e.g. 2,3,4…] by
numbering the longest unbranched chain with the
carboxyl group.
• Greek letters [α, β, γ, δ etc.] are also used in denoting the
positions of substituents on the carboxylic acid chain.
• Position 2 is α; position 3 is β; position 4 is γ etc.
• Example: β-methylpentanoic acid is same as 3-methyl
pentanoic acid [CH3CH2CH(CH3)CH2COOH];
Nomenclature In Carboxylic acids
Contd:
• Aromatic carboxylic acids are also related to the
appropriate HCs
• Examples: benzenecarboxylic acid (benzoic acid); [C6H5-
COOH]
• methylbenzenecarboxylic acid (toluic acid); [CH3-C6H5-
COOH].
C/W:
• Give the structures and alternative names of the following: (i) 2-
methylbutanoic acid (ii) 3-hydroxypentanoic acid,
Answers:

• (i) [CH3CH2CH(CH3)COOH]; Also α-methylbutanoic

acid

• (ii) [CH3CH2CH(OH)CH2COOH]; Also β-hydroxypentanoic

acid,
 Ethers:
Uses [Importance, Applications]
& Properties;
Syntheses / Preparations,
Chemistry and Reactions
Dorcas O. Moronkola CHE 176 Lectures
Contd’
Uses, Importance and Applications of
Ethers
• Most ethers are utilized widely as organic solvents, and as
important media in organic syntheses, reactions and
Industrial processes
• Most common ether is C2H5-O-C2H5 [diethylether/
ethoxyethane= a symmetrical ether] is utilized as solvent.
It was before used as an anesthetic. It is commonly called
ether because of its high Laboratory and Industrial
importance.
• Most ethers are volatile and possess sweet/ acceptable
odour [especially the aromatic ethers]
• Hence they are applied in cosmetics and perfumes
• They have very low flash points; hence they catch fire
very easily in the laboratory, causing fire explosions.
Among the cyclic ethers, TetraHydroFuran
[THF] and epoxyethane are highly important.
THF has reduced volatility, so it is easier and
safer to handle; THF can donate electron pairs
than most ethers and so it is slightly basic,
capable of forming stable complexes with
substances like Grignard reagents (GR). THF
could have been most suitable medium for GRs,
if not for economic reasons, which is recently
produced in commercial amount. O
O
Epoxides are the 3-membered cyclic ethers,
simplest being epoxyethane [ethylene oxide].
It is a colorless low boiling liquid [b.pt=110C],
easily produced on oxidizing ethene at 3000C
using Ag catalyst.
0
[O],Ag Cat.,300 C O
H2C CH2
Alcoholysis of epoxyethane gives many
monoalkyl ethers, with the trade name
‘Cellosolve’. They are important solvents
for varnishes and lacquers.

O
+ HO CH3 H2SO4 Cat.
OH O CH3
Epoxyethane do dimerize in acid catalyst
to ‘Dioxan’- a very useful organic
solvent, which is even miscible with
water.

2 O +
H Cat. O O
Properties of Ethers:
• Ethers are polar, but this polarity only strongly affects physical
properties of smaller members. The heavier or higher molecular
weight members are sufficiently hydrocarbon-like hence they behave
as their all-carbon equivalents of relatively same mol.wt.
• For example the boiling points of diethyl ether (34.5 0C) and pentane
(36.1 0C) are close, and they are only modestly/ partially soluble in
water. [M.wt = 74 & 72 respectively]
Generally ethers are highly flammable, especially the lower aliphatics
which are gases and volatile liquids. They also have characteristic smell
and odour, hence they are utilized in perfumes and cosmetics.
H/W: Give the mol.wt of diethyl ether and pentane . (74,72)
Properties of Ethers Contd:
• Their oxygen atom has unshared pair of electrons, but is not associated
because of unavailability of suitable hydrogen to form H-bonds in their
liquid state. Hence their b.pts is very similar/ comparable to their
counterpart/ equivalent alkanes of relatively same mol.wt, but lower to
the corresponding alcohols of same mass.
• Ethers are generally less soluble in water than alcohols.
• Solubility in water decreases with increase in mol.mass of ethers. For
instance simple ethers such as methoxymethane and methoxyethane, are
less dense than water, and are sparingly soluble in water.
• Therefore as hydrocarbon content of molecule increases, solubility of
ethers decline very rapidly in water.
• The aromatic ethers are quite denser than water.
Preparation / Synthesis of Ethers:
By following (3) methods
(a) Dehydration of alcohols [for preparation of symmetrical ethers]
and
(b)Williamson’s Ether Synthesis [for unsymmetrical and
symmetrical ethers with alkyl and aryl ethers].
(c) Symmetrical ethers formed from warming haloalkanes and dry
silverIoxide.
 (a) Preparation of Ethers by Dehydration of
alcohols
• Ethers are formed from two molecules of alcohol by splitting out (removing) a molecule of
water. Reaction is catalyzed by H2SO4, which takes up water and remove it from the
system.
• CH3CH2-OH + H-OCH2CH3 CH3CH2-O-CH2CH3
2 molecules of ethanol Diethyl ether
• This is a condensation reaction [reaction where water is split out from two substances].

-H2O CH3CH2-O-CH2CH3
CH3CH2-O-H + H-O-CH2CH3
(a) Dehydration of alcohols:
• Symmetrical ethers with lower alkyl groups are prepared on large / industrial scale
for use as solvents by this method, most common and important is diethyl ether.
• The ether is synthesized by reacting alcohols with H2SO4, with removal of H2O
from two molecules of alcohol, like a form of dehydration reaction.
• Recall: under reactions of alcohols, it undergoes dehydration involving elimination
to give an alkene [e.g. ethene is obtained by heating ethanol with conc. H2SO4 to 180
0C].

• Dehydration of two molecules of alcohol to ether rather than to alkene is controlled

by choice of reaction conditions [e.g. diethyl ether is synthesized by heating ethanol
and conc. H2SO4 to 140 0C, with continuous addition of ethanol (the alcohol in
excess)]. A molecule of water is removed from two molecules of alcohol to give the
ether.
• This method is more appropriate for syntheses of symmetrical ethers.
-H2O CH3CH2-O-CH2CH3
CH3CH2-O-H + H-O-CH2CH3
On Mechanism (SN1 or SN2 ) for Ether Synthesis by Dehydration of alcohols:
• Ether formation by dehydration is an example of nucleophilic substitution
with the alcohol playing two roles: protonated alcohol act as substrate,
while the second molecule of alcohol acts as the nucleophile.
• Reaction could be either SN1 or SN2 depending upon whether the
protonated alcohol loses H2O before or simultaneously with the attack by
the second alcohol molecule.
• It will therefore be possible that 20 and 30 alcohols follow SN1 mechanism
in their ether synthesis.
• Likewise n-butanol will give di-n-butyl ether without rearranging, and
presumably without intermediate carbocations, which is (NB) normal for
10 alcohols, which are the least capable of forming C+, but most prone to
back-side attack following the SN2 mechanism.
Summary On Mechanism for Synthesis
of Ethers by Dehydration of alcohols
• Secondary (20) and tertiary (30) alcohols follow SN1
mechanism in their ether synthesis.

• 10 alcohols, which are the least capable of forming

C+, but most prone to back-side attack, follow the
SN2 mechanism.
(b) Williamson’s Ether Synthesis:
• This method is flexible and suitable for preparing both symmetrical and
unsymmetrical ethers.
• Solution of the alkoxide ion is first made, by dissolving Na in
appropriate alcohol. [i.e. 1st the formation of Na alkoxide/ phenoxide]
• An alkyl halide or substituted alkyl halide reacts with the Na alkoxide/
phenoxide.
• Displacement of halogen from haloalkane by the alkoxide or phenoxide
ion occurs.
• The alkoxide act as a nucleophile, and react with the haloalkane to give
the corresponding ether and the leaving group X- / NaX thus:
• Generally:
- + reflux
RX + R'O Na ROR' + NaX
 For example:

H3C OH + Na reflux - +
H3C O Na
Ethoxide ion

- +
H3C O Na + H3C I reflux H3C O CH3 + NaI
Necessary Condition for Williamson Ether Synthesis

•Williamson ether synthesis should be

designed in such a way that the less
hindered alkyl group is provided by the
alkyl halide and the more hindered
(bulkier / branched) alkyl group comes
from the alkoxide ion, as shown below.
• NB: To synthesize an unsymmetrical dialkyl ether, then comes
our choice on how to combine reagents, because one of the
choices is usually better!!!
• For example in the following synthesis of tert-butyl ethyl ether
which choice of combination of reagents is best/ feasible?
CH3

+ - CH3
C2H5Br + Na O CH3 feasible
CH3 H5C2-O CH3

CH3 Not feasible CH3

+ -
H3C Br
+ Na O C2H5

CH3
So which is your choice and
WHY?
In above example, use of tertiary halide is
rejected since it would be expected to yield
mostly or even all as elimination products,
which is not our target/ focus!
Therefore the second choice (not feasible)
[use of tert-butyl bromide with ethoxide ion],
will result to give elimination product, and
not the ether: CH3CH2O + (CH3)3CBr 
-

CH2=C(CH3)CH3 + C2H5OH + Br -
Generally:
RX + M OR  ROR + MX
+ - 1 1

• If R is a secondary or tertiary alkyl group,

elimination occurs leading to formation of an
alkene, which competes strongly with displacement.
• To ensure good yield of the ether you use a primary
alkyl halide (RX).
• Note that there is no restriction on the kind of
alkoxide, the alkoxide could be primary or
secondary or tertiary.
NB: The Williamson ether synthesis is a nucleophilic
substitution reaction.
• It requires a high concentration of a good nucleophile, which indicates
that it is an SN2 reaction. If you want to synthesize an ether such as butyl
propyl ether, you have a choice of starting materials, you can use either a
propyl halide and butoxide ion or a butyl halide and propoxide ion.
• But if you want to synthesize tert-butyl ethyl ether, the starting materials
must be an ethyl halide and tert-butoxide ion.
• If your choice is other way round [use of tert-butyl halide with ethoxide
ion], then you will not obtain the ether. This is because the reaction of a
tert-alkyl halide under SN2/E2 conditions forms only the elimination
product.
.In summary, a Williamson ether synthesis
should be designed in such a way that the
less hindered alkyl group is provided by the
alkyl halide and the more hindered
(bulkier) alkyl group comes from the
alkoxide ion, as shown above.
NB:
• Remember that the alkoxides are not only nucleophiles, but also
strong bases; as bases they tend to react with alkyl halides by
elimination to produce the alkenes.
• Hence whenever we are going to carry out nucleophilic
substitutions, we must be reminded and be aware of the danger
of the competing elimination reaction.
• Always keep in mind that the tendency of alkyl halides to
undergo elimination follows this trend: 30>20>10.
• In above example, the use of tertiary halide is rejected since it
would be expected to yield mostly or even all as elimination
products.
(c) Ethers [symmetrical] are also formed from
warming haloalkanes and dry silverIoxide.

warm
2RX + Ag2O ROR + 2AgX
H/W: Predict the product (ether) of the following
reactions [NB: Present structures and IUPAC names
of products and reactants]:
1. Butanol + Iodopropane ?
2. Propan-2-ol + Iodoethane  ?
3. 2,2-dimethylpropanol + Iodomethane  ?
4. 2-iodo,2-methylpropane + Ag2O  ?
5. Dehydration of 2,3-dimethylbutanol using conc.
H2SO4 at 1400C.
Predict the product (ether) of the following reaction:
1. Butanol + Iodopropane ? (Butyl propyl ether) HOW? [See
below]
2. Propan-2-ol + Iodoethane  ? ((CH3)2CH-O-C2H5) HOW?
3. 2,2-dimethylpropanol + Iodomethane  ? ((CH3)3C-CH2-O-
CH3) HOW?

1. Butanol + Iodopropane ? (Butyl propyl ether)

C4H9OH + Na reflux  C4H9O-Na+ (sodium butoxide)
C4H9O-Na+ + I-C3H7  C4H9O-C3H7 + NaI
Answers
1. Butyl propyl ether
2. (CH3)2CH-O-C2H5
3. (CH3)3C-CH2-O-CH3
4. (CH3)3C-O-C(CH3)3
5. (CH3)2CH-CH(CH3)-CH2-O-CH2-CH(CH3)-CH(CH3)2
Chemistry and Reactions of Ethers:
• Ethers are generally less reactive than alcohols, since they do not
have replaceable H/proton. Ethers do not undergo substitution
with ionic compounds, nor react with metals and strong bases.
Hence ethers are similar to alkanes in their reduced chemical
activity.
• They are mostly utilized as solvents in organic synthesis.
• Chemistry of ethers depends only on O-R part of the molecule.
• The oxygen has two pairs of non-bonding electrons (recall that
ethers lack OH group), making ethers weak Bronsted and Lewis
bases. The oxygen do undergo protonation in acid medium,
where it donates its lone pair of electrons. So ethers act as base.
Chemistry and Reactions of Ethers Contd:
• Ethers are generally less reactive than alcohols / inert,
since they do not have replaceable H/proton.
• Their oxygen [only FG] is sandwiched between two alkyl
groups;
• Are unreactive to bases, dilute acids, reducing agents etc.
Hence they are mostly utilized as solvents in organic
synthesis.
• Ethers with hot conc acids (excess) give the
corresponding alkyl halides [Cleavage reactions i.e.
Nucleophilic substitution reactions]. NB: Mechanisms
and Preparations of Ethers earlier treated.
Chemistry and Reactions of Ethers:
H

+ -
A
:O:
+ HA :O +
R R
R R

Ether O is protonated by the HA strong acid

A nucleophile [A- or X-] can now attack the protonated ether,
and cause cleavage.
H
-
:O:
+ HX :O
+
+ X RX + ROH
weak base & good leaving group
R R
R R
Following reactions occur in ethers:

(a) Cleavage reactions by strong acids

(b) [X]Autoxidations to form peroxides
(c) Complex formation through Grignard reagents

NB: For aromatic ethers, the alkoxy group activates the ring to
have substitutions at 2- and 4-positions.
(a) Cleavage reactions with HX (strong acids):
• This is the major reaction ethers undergo, even though ethers are
comparatively unreactive and stable towards bases, oxidizing and reducing
agents.
• Under vigorous condition [conc. acid and high temperature], the oxygen-
carbon single bond undergoes fission.
• On refluxing ether with concentrated HI, the organic radicals cleave to
form the haloalkanes [iodoalkane]. First an alcohol is formed which reacts
with more HI, to give the iodoalkane. Trend on reactivity: HI>HBr>HCl.
e.g.

HI/reflux H3C I+H C OH

H3C 3
O CH3
• Under mild condition, the alcohol could
be isolated.
• But with more conc. HI, it (the alcohol)
gives the iodoalkane. E.g. below

HI/reflux
H3C OH H3C I
 [X]On Mechanism of Nucleophilic substitution
reactions involved in cleavage reactions of ethers:
• OR group of ethers and OH group of alcohol have nearly the same
basicity, because the conjugate acids of both groups have similar pKa
values. [pKa of CH3OH is 15.5, and pKa of H2O is 15.7]. Both groups
are strong bases, so both are very poor leaving groups.
• Also ethers like alcohols, need to be activated before they can
undergo nucleophilic substitution. Ethers are activated [just like
alcohols] by protonation. Hence ethers undergo nucleophilic
substitution reactions with HI or HBr, though the reaction of ethers
with hydrogen halides is slow [as with alcohols]. Hence the reaction
mixture must be heated to cause the reaction to occur at a
reasonable rate.
NB:
• The oxygen on ether is basic, like O of an
alcohol. Initial reaction between ether and an
acid is the formation of the protonated ether.
• Cleavage then involves nucleophilic attack by
halide ion on this protonated ether, with
displacement of the weakly basic alcohol
molecule.
 H
+ 
:O:
+ HI
:O R I + R' OH

R R' R R'

• [Xr]The OR1 [of the protonated ether] is a poor

leaving group; while the HOR1 is a good leaving
group.
• first step in this mechanism, in which an acid is
one of the reagents, is protonation of the most
basic atom, and in this case is oxygen.
• Protonation converts the very basic –OR1 leaving
group into the less basic R1OH.
 [Xr]Mechanism of Nucleophilic substitution reactions
involved in cleavage reactions of ethers contd’
• In strong HX [HI, HBr] ether cleave to corresponding alcohol
and halide.
• In excess HX, the alcohol formed in the reaction is converted to
the halide.
• This reaction involve ether oxygen to first be protonated
turning the potential leaving group from alkoxide –OR into the
much more easily displaced alcohol HOR.
Mechanism of Nucleophilic substitution reactions involved in cleavage reactions of ethers
contd’

• The displacement is accomplished by the halide ion formed when the

ether is protonated
• This reaction is analogous to reactions of alcohols with haloacids. The
halide ion should be a nucleophile strong enough to do the displacement,
and reaction is subject to limitations of any SN2 reaction. NB: 2nd
equation If SN1 below

H
SN2
CH3:O:CH2CH2CH3 + H
+
H3C +O:CH2CH2CH3 CH3I + CH3CH2CH2OH

protonation -
- nucleophile I attacks less sterically hindered CH
3
I

H SN1 I-
+ +C(CH3)3 I-C(CH3)3
(H3C)3C :O:CH3 + H (H3C)3C +O:CH3
nucleophile attacks
carbocation formed + CH3OH
protonation
What happens next depends on the structure of the ether. If
departure of R1OH creates a relatively stable carbocation
R+ [like tertiary C+], an SN1 reaction occurs, the leaving
group departs, while the halide ion (nucleophile) combines
with the carbocation. Hence here ether cleavage is an SN1
reaction. Tertiary alkyl group tends to undergo SN1
displacement reactions.

H SN1 I-
+ +C(CH3)3 I-C(CH3)3
(H3C)3C :O:CH3 + H (H3C)3C +O:CH3
nucleophile attacks
carbocation formed + CH3OH
protonation
 • [Summary]But if departure of the leaving group would create an
unstable carbocation [like methyl, vinyl, aryl or primary carbocation],
then the leaving group cannot depart.
• Instead it has to be displaced by the halide ion. i.e. an SN2 reaction
occurs. NB: In this SN2 reaction, the halide ion preferentially attacks
the less sterically hindered of the two alkyl groups. Hence the ether
cleavage here is an SN2 reaction.
• Primary alkyl group tends to undergo SN2 displacement.

H
SN2
CH3:O:CH2CH2CH3 +
+
H H3C +O:CH2CH2CH3 CH3I + CH3CH2CH2OH

protonation -
- nucleophile I attacks less sterically hindered CH
3
I
Summary & More on Mechanism of Nucleophilic
substitution reactions involved in cleavage reactions of
ethers contd’
• Cleavage with HI is more rapid than cleavage with HBr because I- is a
better nucleophile than Br-. Harsher conditions must be used if at all HCl
will be employed because Cl- is even a poorer nucleophile. Trend on
reactivity under mild condition: HI>HBr>HCl
• Recall: On refluxing ether with concentrated HI in excess, the organic
radicals cleave to form the haloalkanes [iodoalkanes]. First an alcohol is
formed which reacts with more HI, to give the iodoalkane.
• Use of equivalent/ same amount of HX and ether (i.e. less amount of HX),
makes possible the alcohol formed to be isolated.
• But with more conc. HI which further reacts with the alcohol, to give the
iodoalkane.
[X] Cleavage in Alkyl aromatic ethers:
Alkyl aromatic ethers cleave to produce phenol and
corresponding haloalkane in equivalent amount of HI.
e.g. C6H5OCH3 + HI  C6H5OH + CH3 I

[H/W: Show the mechanism of above cleavage reactions]

Another example: Cleavage Reaction with PCl5

On heating ether with phosphorus pentachloride

[PCl5], cleavage occurs to give the chloroalkanes
(ethylchloride & methylchloride). Example is
C2H5OCH3 + PCl5  C2H5Cl + CH3Cl + POCl3
[X] Summary on Mechanism of Nucleophilic substitution
reactions involved in cleavage reactions of ethers
• Generally, reaction of protonated ether with halide ion, like the
corresponding reaction of protonated alcohol, can proceed either by SN1
mechanism, or by SN2 mechanism depending on the conditions [e.g.
concentration of HX and heat] and structure of the ether.
• Recall the summary: Primary alkyl group tends to undergo SN2
displacement, whereas a Tertiary alkyl group tends to undergo SN1
displacement reactions.
 (b) [X]Autoxidations: Ethers slowly absorb oxygen
to form peroxides when exposed to sunlight. In contact
with air, most aliphatic ethers get converted to their
unstable peroxides. The peroxides are unstable,
dangerously shock-sensitive and explode easily, even
in small concentrations since they decompose with
explosive violence.

R O R' + O2
hv
R O CHR'

HOO
[X]This unwanted oxidation can be
prevented by storing ethers in dark, sealed
bottles in presence of some alcohol.
Peroxides can be removed from ethers in a
number of ways: by washing with solutions
of ferrous ion (Fe2+), which reduces the
peroxides; or distilling from conc. H2SO4,
which oxidizes the peroxides. [NB: In
preparing GR and its reactions, the ether
utilized must be free from traces of water
and alcohol].
(c) Complex formation [through Grignard reagents]. Recall that
diethyl ether [ethoxyethane] is a very suitable solvent for Grignard
reagents. This ether O donate electrons to Mg2+.
CH 3CH 2-O-CH 2CH 3
2H C
CH
+ RMgX R-Mg-X
3 O 3
CH 3CH 2-O-CH 2CH 3
• Other ethers of higher molecular weight are unstable as solvent, for they form complexes
which are insoluble in excess solvent.
• Tetrahydrofuran [THF] have some advantageous properties as an alternative solvent, as it is
better able to donate electron pairs than diethyl ether.
• Recall that THF is slightly more basic and capable of forming more stable complexes with
Grignard Reagent (GR) [NB: pKa of THF= -3.6; pKa of diethyl ether= -2.1].
• [Recall: GR is R-Mg-X, with Mg-C bond largely covalent, and Mg-X totally ionic. These give
the highly reactive Grignard reagent (in ether) wide practical applications for preparing most
homologous series of compounds like HCs, ROHs, RCHOs, RCORs and RCOOHs].
END OF ETHERS
THANK UUUUUU!!!
CHE 176: ORGANIC CHEMISTRY 1
Dr Dorcas O. Moronkola:
Alkoxyalkanes (Ethers), Alkanamines
(Amines), Carbonyl compounds (alkanals
and alkanones i.e. Aldehydes and Ketones
respectively), Carboxylic acids and
derivatives.
[NB: Nomenclatures and Chemistry with
Mechanisms of Reactions, Preparations /
Synthesis and Uses of the Compounds
Discussed in all cases].
Recall: Uses & Properties, Syntheses /
Preparations, Chemistry and
Reactions of

(iii) Carbonyl compounds (alkanals

and alkanones i.e. Aldehydes and
Ketones respectively),
CARBONYLS: CHEMISTRY
OF ALDEHYDES AND
KETONES
Outline on Carbonyls
Introduction to Chemistry of Aldehydes and
Ketones as Carbonyls
Nomenclature/ Naming in Aldehydes &
Ketones [Done earlier]
Importance/ Uses/ Applications of Aldehydes
and Ketones
Preparation/ Synthesis
Chemistry and Reactions of the Carbonyls
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.
Hence (covalent) 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. This affects the chemistry and
reactions of carbonyl compounds.
The carbon atom in C=O is slightly electron deficient.
Hence electron-rich reagent (Z:) – Nucleophiles (bases)
easily form bonds with the carbonyl carbon. So 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.
Aldehydes and ketones are usually
referred to as the carbonyl compounds.
There are other classes of organic
compounds with carbonyl in their
functional group. Others includes
esters/ alkanoates [RCOOR’],
carboxylic acids [RCOOH], anhydrides
[RCO-O-COR’], acyls [RCO-], and
amides [-CONH-].
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.
Aldehydes have a single H attached to the
carbonyl carbon, and are usually terminal i.e. at
one of the end positions, hence taking no 1
when numbering; but ketones have two
hydrocarbon groups bonded to the carbonyl
carbon, and are never terminal. O
O
R R'
R H Ketone
Aldehyde
Aldehydes oxidize more easily
and are more susceptible to
nucleophilic addition reactions.
Generally aldehydes are good
reducing agents and are more
reactive than ketones.
 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 O H
• benzaldehyde in almond;
• vanillin [3-methoxy, 4-hydroxy-benzaldehyde] in vanilla beans
OCH3
OH

• cinnamaldehyde [3-phenyl-2-propenal] in cinnamon.

O
H
Importance, Uses and Applications of some Ketones
Propanone [acetone]
• as solvent; in rubber cement and paints, and as nail-polish removers
• body produce propanone during fasting, in uncontrolled diabetes, and high-protein diets
when large amounts of fats are metabolized for energy
O
Butanedione
CH3
• One of the unappealing odor of armpits and sweaty feet H C 3
O
CH3

Carvone O

• flavour compound in oil of spearmint.

CH3

H3C CH2

Menthone in flavouring
O

H3C CH3

Muscone CH3
• in musk perfumes O
O

Cyclohexanone
• intermediate in manufacturing of other chemicals; used in one stage of nylon production.
Preparation/
Synthesis of the
Carbonyls
[Aldehydes and
Ketones]
Preparation of Alkanals/ Aldehydes and
Alkanones/ Ketones from Oxidation of
Alcohols:
• Recall: Trend of oxidation of 10, 20, 30 alcohols
respectively giving following:
• Primary [10] alcohol [RCH2-OH]  Aldehyde
[RCHO]  carboxylic acid [RCOOH].
• Secondary [20] alcohol [RR1CH-OH] 
Ketone [RR1CO].
• Tertiary [30] alcohol [RR1R11C-OH]  No
reaction
Notice that in the oxidation of both primary and
secondary alcohols (see chart above), one H is
removed from the carbon to which the OH is
attached. But in tertiary alcohol the carbon
bearing the OH group is not bonded to any H,
hence the OH in tertiary alcohols cannot be
oxidized to a carbonyl group.

Above trend is termed oxidation because number

of C-H bonds in the reactants decreases, and the
number of C-O bonds increases.
Reagents often used in oxidizing alcohols is H2CrO4
(chromic acid), which is formed from CrO3 (chromium
trioxide) or Na2Cr2O7 (sodium dichromate) dissolved in
aqueous acid.
Secondary alcohols are oxidized to ketones, while tertiary
alcohols usually are not further oxidized.

Examples:
(i) CH3CH2CH(OH)CH3 + (CrO3/H2SO4(aq)) → CH3CH2C=OCH3
Butan-2-ol Butanone

(ii) Cyclohexanol + (Na2Cr2O7/H2SO4(aq)) → Cyclohexanone

H/W: Show the structure and
name of the product formed from
the reaction of the following
alcohols with Na2Cr2O7/H2SO4(aq).
(1) 3-hexanol (2 alcohol)
0

(2) 2-methyl-2-pentanol (3 alcohol) 0

(3) 2,4-hexanediol(dione formed from the two 2 alcohol)

0

(4) 1,4-butanediol (1,4-butanedioic acid from the two 1

0

alcohols)
•Aldehydes are formed from the oxidation of primary alcohols.
e.g.
OH [O]
H3C O
H3C H
Propanol
Propanal
If the 10 alcohol is not refluxed with oxidizing agent, the
aldehyde can be collected. But with refluxing, the aldehyde
formed is itself oxidized to carboxylic acid. These show that
aldehydes are good reducing agents i.e. they are easily
oxidized to acids. NB: In the presence of more oxidizing
reagent propanal formed above further oxidizes to
propanoic acid.
Oxidizing Agents In Preparation of
Carbonyls
A. H2CrO4 (chromic acid), formed from CrO3 (chromium trioxide)
or Na2Cr2O7 dissolved in aqueous acid [CrO3/H2SO4(aq)/
Na2Cr2O7/H2SO4(aq)]
B. Utilizing pyridinium chlorochromate (PCC) as the oxidizing
agent in dichloromethane (CH2Cl2), which also stop oxidation of
primary alcohol at the aldehyde
C. Swern oxidation of alcohols utilizing dimethyl sulfoxide
[(CH3)2SO], oxalyl chloride [(COCl)2], and triethyl amine
[(C2H5)3N]. Better method since above chromium-based reagents
are toxic. Also reaction is not carried out in an aqueous solution,
and the oxidation of primary alcohol stops at the aldehyde
D. Oxidative Cleavage of 1,2-diols with periodic acid (HIO4)
E. Oxidative cleavage of alkenes (ozonolysis), under either
[reducing agent like Zn or dimethyl sulfide (CH3)2S] or
[oxidizing agent like hydrogen peroxide (H2O2)]
F. Preparation of carbonyls from dihalides
G. OTHERS
A. Below is complete oxidation of
butanol:

H
OH
H2CrO4 further
CH 3CH 2CH 2CH 2OH H3C O
butanol oxidation H3C O
butanal butanoic acid

Generally if the primary (10) alcohol is not refluxed with oxidizing agent, the aldehyde
can be collected. But with refluxing, the aldehyde formed is itself further oxidized to
carboxylic acid.
These show that aldehydes are good reducing agents; they are easily oxidized to acids.
B. Utilizing pyridinium chlorochromate (PCC) as the
oxidizing agent in dichloromethane (CH2Cl2), which also
stop oxidation of primary alcohol at the aldehyde

The oxidation of primary alcohol [e.g. butanol] will stop

at the aldehyde if pyridinium chlorochromate (PCC) is
used as the oxidizing agent in solvents like
dichloromethane (CH2Cl2).

PCC
CH3CH2CH2CH2OH H3C O
primary alcohol CH2Cl2 aldehyde
C. Swern oxidation of alcohols
• It uses dimethyl sulfoxide [(CH3)2SO], oxalyl chloride
[(COCl)2], and triethyl amine [(C2H5)3N].
• Swern oxidation is one of the better method developed. It is
not chromium-based; it is less toxic.
• Use of chromium-based reagents are toxic, hence this
method of oxidation of alcohols have been developed.
• Since the reaction is not carried out in an aqueous solution,
the oxidation of a primary alcohol stops at the aldehyde, as
in PCC oxidation shown above.
• Secondary alcohols are also oxidized to ketones.
 H
1. (CH3)2S=O, [(COCl)2], -60 °C
CH3CH2CH2OH H3C
primary alcohol 2. (C2H5)3N O
aldehyde

H3C
1. (CH3)2S=O, [(COCl)2], -60 °C
CH 3CH 2CH(OH)CH 3
secondary alcohol 2. (C2H5)3N CH3
ketone
D. Oxidative Cleavage of 1,2-diols
with periodic acid (HIO4)
 D. Oxidative Cleavage of 1,2-diols with periodic acid (HIO4): Recall: 1,2-diols are
obtained from hydroxylation of alkenes; the alkene is oxidized to 1,2-diol either
by KMnO4 in cold basic solution or by osmium tetroxide (OsO4) to form the
vicinal diols/ glycols. 1,2-diols are now oxidized to ketones or aldehydes or both
by periodic acid HIO4. Reaction occurs because iodine is in a highly positive
oxidation state (+7), hence it readily accepts electrons. Periodic acid reacts with
diol to form a cyclic intermediate. As the intermediate breaks/ cleaves, bond
between the two carbons bonded to the oxygens breaks. If a carbon that was
bonded to an OH group is also bonded to two R (alkyls) groups, then the product
will be a ketone; If the carbon is bonded to a R and a H, then the product will be
an aldehyde. Since this oxidation cuts the reactant [1,2-diol] into two pieces, it is
called an oxidative cleavage.
H3C
OH H3C
CH3 H3C H3C
HIO4 CH3
H3C
H3C C=O + C=O + HIO 3
OH
2-methyl-1,2-butanediol
3-methyl-2,3-butanediol
O
O
+ H2 O
H3C H
I ketone (propanone) aldehyde (ethanal)
O O
OH
cyclic intermediate
 H3C
OH H3C
CH3 H3C H3C
HIO4 CH3
H3C
H3C C=O + C=O + HIO 3
OH
3-methyl-2,3-butanediol
2-methyl-1,2-butanediol
O
O
+ H2 O
H3C H
I ketone (propanone) aldehyde (ethanal)
O O
OH
cyclic intermediate
 Another Example on Cleavage
with HIO4:

CH3 O
OH HIO4 ketone
CH3 + HIO 3
OH H
1-methyl-1,2-cyclohexanediol
aldehyde
O

[Product is heptanal with 6-one].

E. Oxidative cleavage of alkenes
(ozonolysis):
• Alkenes can be directly oxidized to carbonyl compounds
by ozone (O3) or by KMnO4. At low temperature on
treating alkene with ozone, its double bond breaks and
carbons that are doubly bonded to each other (.>C=C<)
are now doubly bonded to oxygen instead. This oxidation
reaction is referred to as ozonolysis. i.e

1. O3, -78 °C
>C=C<
-
>C=O + O=C<
2. work up
[X] Ozone and alkene undergo a concerted
cycloaddition reaction, where the O atoms add to the
two sp2 carbons in a single step. An electrophile add
to one of the sp2 carbons, while a nucleophile adds to
the other. Electrophile is the O at one end of ozone
molecule, and nucleophile is the O at the other end.
Product of ozone addition to alkene is called a
molozonide i.e. one mole of ozone has added to the
alkene. Molozonide is unstable because it has two O-
O bonds which immediately rearranges to more
stable ozonide. Ozonide are not isolated since they
are explosive. In solutions they are easily cleaved to
carbonyls.
When ozonide is cleaved in presence of reducing agent like Zn or
dimethyl sulfide [(CH3)2S] products will be ketones, aldehydes or
both. Product will be ketone when the sp2 carbon of alkene is bonded
to two carbon-containing substituents;
Product will be an aldehyde if at least one of the substituents bonded
to the sp2 carbon is a hydrogen. The reducing agent prevents
aldehydes from being oxidized to carboxylic acids. Cleaving the
ozonide in the presence of Zn or dimethyl sulfide is referred to as
working-up the ozone under reducing conditions.
R R
R R
O
Zn, H2O
C=O + C=O
H or (CH3)2S
R O reducing condition H
O R
ketone aldehyde
ozonide
But if ozonide is cleaved in presence of an oxidizing agent
like hydrogen peroxide (H2O2), the products will be
ketones, carboxylic acids, or both. Carboxylic acids are
formed instead of aldehydes because the aldehyde initially
formed will immediately oxidize to carboxylic acid by the
H2O2. Cleavage in the presence of H2O2 is called working
up the ozonide under oxidizing conditions.
R R
R R
O
H2O2
C=O + C=O
H
R O oxidizing condition HO
O R
ketone carboxylic acid
ozonide
C/W & H/W: Predict ozonolysis products of
(i). 3-methylhex-3-ene under H2O2 at -78 0C;
(ii). Hex-3-ene under (CH3)2S at -78 0C;
(iii). 2-methylcyclohexene under Zn/ H2O,at -78 0C;
(iv). 1-pentene under Zn/ H2O,at -78 0C;
(v). 1-pentene under under H2O2, at -78 0C].
NB: One carbon fragment obtained from the
reaction of a terminal alkene with ozone will be
oxidized to methanal (formaldehyde) if the
ozonide is worked up under reducing conditions,
and to methanoic acid, if it is worked up under
oxidizing condition. [see yourself in Qs (iv & v)]
ANSWERS
(i) Ozonolysis of 3-methylhex-3-ene under H2O2 at -
78 0C: i.e. at oxidizing condition yield butanone
and propanoic acid
(ii) Ozonolysis of Hex-3-ene under (CH3)2S at -78 0C:
i.e. under reducing condition yield only propanal
(iii) Ozonolysis of 2-methylcyclohexene under Zn/
H2O,at -78 0C: i.e. under reducing condition yields
heptanal, 6-one.
(iv) 1-pentene under Zn/ H2O,at -78 0C: i.e. at
reducing condition Yields methanal + butanal
(v) 1-pentene under under H2O2, at -78 0C]: i.e. at
oxidizing condition Yields methanoic acid + butanoic
acid
 F. Preparation of carbonyls from
dihalides:
• When there are two halogen atoms bonded to same
carbon at end of chain, on hydrolysis it yields aldehydes
e.g. as in 1,1-dichloroethane below.
• Mild alkali like Ba(OH)2(aq) may be used for the
hydrolysis.

OH
H2O/ Ba(OH)2 -H2O
CH3CHCl2 H3C CH3CHO
OH
1,1-dichloroethane unstable ethanal (aldehyde)
 If the two halogens are on a carbon in
the middle of the chain, then a ketone is
formed e.g.
H3C H3C
Cl H3C OH
H2O/ Ba(OH)2 -H2O
C C=O
H3C OH
H3C Cl unstable H3C propanone
2,2-dichloropropane

H/W: Predict products of reaction of H2O/

Ba(OH)2 with each of the following:
(i). 2,2-dichlorobutane
(ii). 1,1-dichloropropane [PTO]
 If the two halogens are on a carbon in
the middle of the chain, then a ketone is
formed e.g.
H3C H3C
Cl H3C OH
H2O/ Ba(OH)2 -H2O
C C=O
H3C OH
H3C Cl unstable H3C propanone
2,2-dichloropropane

H/W: Predict products of reaction of H2O/

Ba(OH)2 with each of the following:
(i). 2,2-dichlorobutane [butanone]
(ii). 1,1-dichloropropane [propanal]
Chemistry and
Reactions of the
Carbonyls
[Aldehydes and
Ketones]
Nucleophilic addition reaction can be perceived thus:
-
Recall the carbonyl group is polar O
+
C
and it is flat. So it is susceptible to attack R
R
from below and above. The pie (π) electrons
spend more time with the oxygen
[Cδ+---Oδ-]. Also the H on the α-C is acidic.
Hence there is easy attack of a base [Z:] on
the carbon of the C=O. This illustrates the
addition reaction aldehyde and ketone
undergo.
O Z: Z: Z:
A H A ....... ä- A O
-
+ H2 O A OH
O
Z: H H H
The main feature of the nucleophilic attack on
the carbonyl group is the attacking group ‘Z’
bonding to the carbon atom. Then the pie [π]
bond to the oxygen atom breaks. The oxygen
atom then have the ability to make a sigma bond
[δ] to another species, usually a H ion. Rather
than displace another group which usually
happen in nucleophilic attack, the attacking
nucleophile adds to the C=O of the aldehyde or
ketone. Therefore this type of reaction is called
nucleophilic addition reaction.
 On Chemistry/ Nucleophilic Addition
Reactions of Aldehydes and Ketones
• 1. Reactions with Tollen’s Reagent
• 2. Reactions with derivatives of ammonia [H2N-Y]
[NB: 2,4-dinitrophenylhydrazine] [Condensation]
• 3. Reactions with Cyanides → Cyanohydrins
• 4. Reactions with Grignard Reagents [RMgX]
• 5. Reactions with alcohol → Acetal formation
• 6. Reduction reactions [LiAlH4 etc]
• 7. Reactions with Fehling’s solution
• 8. Iodoform tests for C=Os
• 9. Clemmenson’s reduction
• 10. Polymerisation reactions [Leave out]
[X] Recall the oxidation of aldehydes give
carboxylic acids

KMnO4/K2Cr 2O4
RCHO RCOOH
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(NH3)2 + 3OH 2Ag + CH3COO + 4NH3
Silver mirror
[X] 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. NB: Ketones are
hard to oxidize.
2. Addition of derivatives of Ammonia [H2N-Y]:
The lone pair on N of ammonia and derivatives easily
add to C=O on aldehyde and ketone. Product formed
is not very stable with ammonia, but other derivatives
of ammonia form useful products with the C=O. The
reaction is also known as condensation reaction, since
water is released. Generally following occurs:

A
G A A
G _
_ N Y + H2O
+ H2N Y _ _
NH Y G
O HO
Derivatives formed i.e. Nature of [H2N-Y]:-
A
_
Condensation Product N Y
G
H2N-OH Hydroxylamine Oxime

H2N- NH2 Hydrazine Hydrazone

H2N-NHC6H5 Phenylhydrazine Phenylhydrazone
H2N-NHCONH2 Semicarbazide Semicarbazone
Benzaldehyde form benzaldehyde
phenylhydrazone with phenylhydrazine
Thus: H O
H NNHC 6H5

+
_ H
+ H2N NHC 6H5 + H2O

i.e
.

H +
_ H H
+ H2N NHC 6H5 + H2O
O NNHC 6H5
Benzaldehyde phenylhydrazine
Benzaldehyde phenylhydrazone
The products above are useful in
identification of the aldehyde or ketone.
Recall your 2,4-dinitrophenylhydrazine,
which is orange in colour, reacts with
aldehyde or ketone to give orange-
yellow colour/ solid, which is its 2,4-
dinitrophenylhydrazone, possessing
characteristic m.pt. The result can be
used to characterize and identify the
C=O.
 C/W
Write out the condensation derivatives formed from the reaction of each
of the following [H2N-Y] with a (a) named aldehyde [see examples below]
(b) named ketone i.e.

A
G A A
G _
_ N Y + H2O
+ H2N Y _ _
NH Y G
O HO
H2N-OH Hydroxylamine
H2N- NH2 Hydrazine
H2N-NHC6H5 Phenylhydrazine
H2N-NHCONH2 Semicarbazide

O H

O
O
H3C O
H3C CH3 CH3
H3C
H O
H3C CH3
H3C
3. Addition of Cyanide [Cyanohydrin
formation]
• Addition of cyanide to carbonyls gives the
Cyanohydrin. The method is useful for making
mixed acids and alcohols. The α-carbon to
nitrile group is with alcoholic OH in the
Cyanohydrin. The CN of the Cyanohydrin can
be hydrolyzed to the corresponding carboxylic
acid [Recall under preparation of acids]. NB:
There is additional C in product compared to
the starting carbonyl.
A
G + A
H G
-
+ CN
CN
O HO
Cyanohydrin
Examples of cyanohydrin:
(i) For ketone C=O

H3C
CH3 H3C CH3
H2SO4 CH3 H O/H SOH3C CH3 -H 2O
2 2 4 H2C COOH
+ NaCN
CN COOH
O HO HO -
Propanone Propanone cyanohydrin 2 methylpropenoic acid
Examples of cyanohydrin:
(ii) For aldehyde C=O
O - + +
CN ,H
H3C CH 3CH(OH)CN H CH 3CH(OH)COOH
ethanal H 2hydroxypropane nitrile 2hydroxypropanoic acid

The acid is also called lactic acid, which

is produced when milk goes sour. The
acid is industrially formed naturally by
actions of the bacteria- Bacillus acidi
lactic on sugars. Acid produced is utilized
in dyeing and leather industries.
Examples of cyanohydrin:
(iii) For aromatic aldehyde
H H
H NaCN, NaHSO
3
CN H2O,HCl COOH
Hydrolysis
O OH OH
Benzaldehyde nitrile acid
4. Reactions of Carbonyls with Grignard Reagents
RMgX [GR]
Addition of Grignard reagent to carbonyl compounds
lead to formation of new C-C bonds. The reaction
yields a number of products depending on the
structure of the carbonyl and structure of the
Grignard reagent. NB: GR are prepared under
anhydrous conditions, adding alkyl halide to Mg(s)
(magnesium shavings) in ether (e.g. diethyl ether).
E.g. bromoethane → ethylmagnesium bromide
Mg
CH 3CH 2Br CH 3CH 2MgBr
(C2H5)2O
The GR reacts as if it were a carbanion,
hence the nucleophile is a strong base.
- +
CH3CH2MgBr reacts like CH3 CH2 Mg Br
Consequently also, aldehydes and ketones undergo
nucleophilic addition reactions with GR.
 GR will react with the carbonyl carbon to form an
alkoxide ion which complex with magnesium ion.
On addition of water or dilute acid, the complex
breaks up to form the appropriate alcohol.
GR will react with methanal to give a primary
alcohol as the addition product.

O
- + H3O+
+ CH 3CH 2CH 2CH 2-MgBr CH 3CH 2CH 2CH 2CH 2O Mg Br CH 3CH 2CH 2CH 2CH 2OH
0
butylmagnesium bromide alkoxide ion 1-pentanol (1 alcohol)
H H
methanal
Other aldehydes will react with GR to
produce secondary alcohols.

- + OH
O Mg Br
O

+ CH 3CH 2CH 2-MgBr

H3O+
propylmagnesium bromide
H3CH 2C H H3CH 2C CH 2CH 2CH 3 H3CH 2C CH 2CH 2CH 3
0
propanal alkoxide ion 3-hexanol (2 alcohol)
 GR will react with ketones to give
tertiary alcohols as the addition
products.

- + OH
O Mg Br
O

+ CH 3CH 2-MgBr
H3C
H3O+ H3C
ethylmagnesium bromide
H3CH 2C CH 2CH 2CH 3
H3C CH 2CH 2CH 3 H3CH 2C CH 2CH 2CH 3
0
2-pentanone alkoxide ion 3-methyl-3-hexanol (3 alcohol)
In a shorter form (not showing the
complex/ alkoxide), numbers can be used
to indicate the two steps, taking place in
the order of use. i.e. GR first fully react
with the carbonyl before the acid is added.
E.g.
OH
O
1. CH3MgBr

2. H3O+ H3C

H2CH3C CH2CH3 H3CH2C CH2CH3

3-pentanone 3-methyl-3-pentanol
C/W: What product will be formed
when
(i) phenylmagnesium bromide
(ii) pentylmagnesium bromide
separately react with each of
the following carbonyls?
(a) Hexanal
(b) 3-Heptanone
(c) cyclohexanone
C/W Answers: What product will be formed when
(i) phenylmagnesium bromide (a)[C5H11CH(OH)-
Ph] a 20alcohol ; (b)[(C2H5)(C4H9)C(OH)-Ph] a
30alcohol ; (c)[1-phenylcyclohexanol] a
30alcohol
(ii) pentylmagnesium bromide[C5H11MgBr]
separately react with each of the following
carbonyls? (a)[C5H11CH(OH)-C5H11] a 20alcohol;
(b)[(C2H5)(C4H9)C(OH)-C5H11] a 30alcohol ;
(a) Hexanal
(b) 3-Heptanone
(c) cyclohexanone
5. Addition reactions with alcohols: It
leads to acetal (diether) formation and
the reaction is mainly for aldehydes.
RCHO easily add to alcohols once the
reagents are dry. HCl acts as catalyst.
Generally:
A G
G
OR
+ 2ROH A + H2O
O OR
diether[acetal]
Most common is the addition of ethanol to
ethanal, to give the ether 1,1-diethoxy
ethane usually referred to as the acetal.

O
H3C + 2C2H5OH dryHCl CH3CH(OC2H5)2 + H2O
H -
ethanal 1,1 diethoxyethane
6,7,8,9. Reduction Reactions
of Aldehydes and Ketones
6. Aldehyde and ketone can be reduced to
primary and secondary alcohols
respectively using H2/Ni or LiAlH4 [lithium
tetrahydridoaluminate(III)] as catalyst.

O +
H3C H ,LiAlH 4 CH CH OH
3 2
ethanal H ethanol
 LiAlH 4,HCl
CHO CH 2OH

benzaldehyde phenylmethanol
Benzyl alcohol

H3C
CH3

H2/Ni CH3CHOHCH3
O propan-2-ol
Propanone
7. Reactions with Fehling’s solution:
Aldehydes are capable of reducing
2+ +
Cu 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.
8. Iodoform tests for C=Os:
Ketones are less easily
oxidized, but it
undergoes the
‘iodoform reaction’.
[See below].
8. The 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
9. Further studies:
Check Wolff-Kishner and
Clemmensen reductions.
 CH2CH2CH3
O ngCl
CCH2CH3 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.
H/W or C/W:
What will Reactions of
Zn/Hg/HCl(aq) (Clemmensen
reduction) with each of the
following give?
(a)Benzaldehyde
(b)Butanone
(c)2-Hexanone
CHE 176: ORGANIC CHEMISTRY 1
Dr Dorcas O. Moronkola:
Alkoxyalkanes (Ethers), Alkanamines
(Amines), Carbonyl compounds (alkanals
and alkanones i.e. Aldehydes and Ketones
respectively), Carboxylic acids and
derivatives.
[NB: Nomenclatures and Chemistry with
Mechanisms of Reactions, Preparations /
Synthesis and Uses of the Compounds
Discussed in all cases].
Recall: Uses & Properties, Syntheses /
Preparations, Chemistry and
Reactions of

(ii) Alkanamines (Amines),

 PROPERTIES OF AMINES:
• Simple aliphatic amines (alkanamines) are gases, with
characteristic ammonia smell; moderately higher amines
are liquids with distinctive fishy odour; the relatively very
high molecular weight amines are solids
• Since they are polar compounds, apart from ammonium
compounds, amines are capable of forming
intermolecular hydrogen bonds with each other, hence
leading to increase in their boiling points compared with
their counterparts having similar molecular weight that
are less polar
• Boiling points of isomeric amines decrease from primary
amine to secondary amines i.e. volatility is enhanced by
branching, the more the branching the lower the boiling
point
PREPARATION / SYNTHESIS OF AMINES:
• Industrial sources
• Synthesis / Preparations –
• (1) Hofmann degradation of Amides
• (2) Reduction of nitriles
• (3) From haloalkanes
• (4) Reductive Amination of C=Os
• (5) Synthesis of the aromatic amine – Phenylamine i.e.
Aniline
Industrial sources of Amines:
• The methylamines are obtained by passing methanol and
ammonia over aluminium oxide catalyst on an inert
support at about 400 0C, under high pressure. The
dimethylamine is the most important, because it is utilized
in the manufacturing of synthetic fibre solvents,
unsymmetrical dimethylhydrazones and other industrially
important compounds; also as fuels in jets and rockets
• Benzene is nitrated and reduced to phenylamine thus: [see
equations]
• Aromatic amines are sometimes prepared starting from
chlorobenzene
SYNTHETIC PREPARATIONS OF AMINES:
• [NB: Features of each method below]
• (1) Hofmann degradation of amides: Method give good
yields of primary amines; It involve warming the amide
with bromine and conc. Alkali.
• (2) Reduction of (a) nitriles (b) oximes: It involve reduction
treatment of the nitrile / oxime using LiAlH4 in
ethoxyethane (diethyl ether). Alternatively Na in absolute
alcohol (e.g. ethanol) can be used.
(3) Synthesis of Amines From
Haloalkanes:
• Good method for synthesizing higher alkylamines, by
reacting haloalkanes with excess alcoholic ammonia under
pressure in sealed tubes. The rate of this reaction becomes
progressively quicker because the alkylamines are more
reactive than ammonia
• Hence the reaction is not generally convenient for
preparing individual amines, more so in this system each
amine exist in equilibrium with their salts.
(4) Synthesis of Amines by Reductive
Amination of Carbonyls (C=Os) (aldehydes
and ketones):
• The C=O compound react with H2 and ammonia over
nickel-chromium catalyst at high temperature
• We can use the same method to successfully prepare /
synthesize appropriate amine from benzaldehyde thus:
(5) Synthesis of Aromatic Amine –
Phenylamine i.e. Aniline:
• From the reduction of nitrobenzene utilizing tin and conc.HCl,
(X)where tin is added little at a time during refluxing; tin(II)
chloride is formed, which acts as the principal reducing agent,
itself being oxidized to salt of tin(IV), which forms a complex
acid with HCl and combines with the phenylamine formed;
• The targeted phenylamine is liberated from the double salt by
treating with excess conc. NaOH.
• It requires quite large amount of NaOH to form tin(IV)
hydroxide, which precipitates out, then dissolves as
hexahydroxostannate(IV) ions when the solution is strongly
alkaline; after which the phenylamine is extracted by steam
distillation.
• This method is not economical, since tin is expensive, instead it
is more economical to use iron turnings.
Chemistry and Reactions of Amines:
• Amines generally are the most common organic bases
with electron-rich functional group;
• the Alkanamines are much stronger Lewis bases because
of their ability to donate the electron pair on their N to a
proton, hence they are stronger bases than ammonia.
• RNH2 + H2O ⇋ RNH3+ + OH- while
[NH3 + H2O ⇋ NH4+ + OH- ]
• Basic strength of amines is determined by 2/TWO
important factors:
Chemistry and Reactions of Amines Contd’:
• Basic strength of amines is determined by 2/TWO important factors
thus:
(1) availability of electron pairs to be donated to a proton;
(2) the ease at which protonated amine can undergo solvation with
water molecules, so as to be stabilized;
NB: the release of electron pairs for donation is determined /
supported by electron-donating effect, hence the following
decreasing trend in basic strength is expected:
30 amine > 20 amine > 10 amine > NH3
Chemistry and Reactions of Amines
Contd’:
Since solvation is made easier and favored by H-bonding
between amine’s H atom on its N, and O atom of the water, we
expect that the following ease of solvation of protonated
amines decreases in the following trend:
NH3 > 10 amine > 20 amine > 30 amine
Now combining the above two, [electron-pair donation and
ease of solvation effects], basic strength of amines will
therefore increase in the following order:
20 amine > 10 amine > 30 amine > NH3 [NB]
NB: Basic strength of amines can be modified by different
electron-donating inductive power/ donation of different /
various alkyl groups, though the steric hinderance of bulky
groups may come to display, and have effect of impairing
reactivity despite favourable electronic effects.
Chemistry and Reactions of Amines Contd’:
• Above summarises that aliphatic amines are stronger bases than ammonia.
• But phenylamine (aniline) is a much weaker base than ammonia. This can
be explained thus:
the positive charge acquired on protonation is widely distributed among
the alkyl group(s) of aliphatic amines, unlike in phenylammonium
(anilinium) ions [C6H5NH3+] that has its charge localized in the region of
the N atom, and it is not distributed about the ring (in the way negative
charge possessed by phenoxide anion does).
Introduction of nucleophilic substituents like OH and CH3O on the ring of
phenylamines especially at the 4-/p- positions can increase its basic
character since it causes an increase in the electron-density about the ring.
The effect is transmitted to the amino group, making its N atom much
richer in electrons, hence making the phenylamine derivatives more basic.
Also protonation of the amino group on phenylamine has significant effect
on its directing powers: especially in a strongly acidic medium, it leaves
only the inductive effect operating. So for electrophilic substitution, the
cation now directs predominantly to the 3-/m- position, owing to the
deactivation of the ring.
H/W and Practising Questions
• To be given in class
Reactions of Amines:
• Salt formation
• Acylation (Amide formation); [cf COOHs]
• Isocyanide (Carbylamine) Test for Primary Amines [cf Practicals
CHE191]
• Formation of Quaternary Ammonium Salts
• Reaction with Nitrous Acid
• Diazotization (Nitrosation) / Coupling reactions [cf Practicals CHE191]
Lectures on Chemistry and each bullet on
Reactions of Amines
• Details to be studied together in class.
• Be in Class for their discussions please!
CHE 176: ORGANIC CHEMISTRY 1 Carboxylic Acids
[COOHs] & Derivatives Dr Dorcas O. Moronkola:
Introduction to its Chemistry
Nomenclature/ Naming in COOHs [Done
earlier]
Importance/ Uses/ Applications of COOHs
Preparation/ Synthesis
Chemistry and Reactions of Carboxylic acids
Derivatives of COOHs
 On Chemistry of Carboxylic Acids
• Structure
• H-Bonding
• Physical properties
• Industrial/ Commercial preparations
• Synthesis / Preparation (Oxidation of primary alcohols; GR
synthesis involving carbonation; Hydrolysis of nitriles;
Hydrolysis of esters involving saponification; Cannizaro
reaction; Synthesis of benzenecarboxylic acids / benzoic acids
from methylbenzene and its derivatives)
• Reactions (Role/ effect/ importance of the medium on acidic
properties; Salt formation; Esterification; Halogenation;
Conversions into acyl chlorides; Reduction; Amide formation)
• DERIVATIVES [i.e. Acid chlorides, Anhydrides; Esters and
Amides]
 Structure of Carboxylic Acids
•As seen in other carbonyls (aldehydes,
ketones etc.), there is mesomeric
withdrawal of electrons away from ‘C’
atom towards the more electronegative
‘O’ atom in the carbonyl bonding of
carboxylic acids, leading to a relatively
positive charge on ‘C’ atom
•Electron deficiency on the ‘C’ atom
results in inductive pull of electrons
away from the H of the O-H bond
•(show structure)
Structure of Carboxylic Acids Contd
• This intensify the stability of the carboxylate anion
‘RCOO-, therefore enhancing removal of a proton (H).
[NB: This is not the case in alcohols, where it is more
difficult to remove a proton ‘H’, hence have weaker
acidic property compared to carboxylic acids]
• The carboxylate anion exist as resonance hybrid, where
the π (pie) electrons are delocalized about the two C to
O bonds, making them to be equivalent.
• (see structures- The carboxylate anion).
 On H-bonding in Carboxylic Acids
• The simplest carboxylic acids (methanoic and ethanoic
acids) exist mostly as a dimer, demonstrating the high
possibility/ ease of forming two strong H-bonds in the
dimeric forms
• The highly polar carboxylic acids dimerize in liquid phase
and in non-aqueous solvents like CCl4, forming two H-
bonds between the pair of molecules
• (see structure)
 H-bonding in Carboxylic Acids Contd

• Ease of dimer formation in carboxylic acids accounts for the observed

high boiling points in carboxylic acids, compared to alcohols having
similar molecular masses by as much as 20 0C higher
• (see table)
• NB: In water and other hydroxylic solvents the dimers dissociate into
their monomeric forms.
Compound CH3COOH CH3CH2CH2OH CH3CH2COOH CH3CH2CH2CH2OH

Rel. Mol. 60 60 74 74
mass
Boiling point 118 97 141 117
(0C)
 Physical properties of carboxylic acids:
• Most (up to C10 members) are liquids at room
temperature
• Ethanoic (acetic) acid freezes below 17 0C to an ice-like
solid referred to as ‘Glacial ethanoic/ acetic acid’
• Lower members have sharp pungent odour
• The 1st four aliphatic members [methanoic, ethanoic,
propanoic and butanoic acids] are highly miscible with
water (likewise the simple alcohols), since the FGs form H-
bonds with water; since covalency characterizes higher
members due to their higher HC content, they are
progressively less soluble in water; Aromatic
benzenecarboxylic (benzoic) acid is slightly soluble in
water, but readily soluble in hot water
• Carboxylic acids dissolve in appropriate organic solvents
Physical properties of carboxylic acids
contd:
• Boiling point (0C) increases with increase in relative
molecular mass down the group like in all homologous
series of compounds
• Aromatic acids compared to their aliphatic counterparts
exist as crystalline solids with higher melting points (M.pt)
• In the aliphatic series, members with even number of ‘Cs’
have higher M.pts than their members with odd number
of Cs; Structural elucidation utilizing X-ray analysis show
this is related to packing of the crystals in the solid
• Density decreases with increasing relative molecular mass
On Industrial/ Commercial preparations of
–COOHs:
• The following 3 will be studied because of their
importance and uses
• methanoic, ethanoic and benzencarboxylic (benzoic)
acids
• i.e. [HCOOH, CH3COOH, C6H5COOH]
Synthesis / Preparation of Carboxylic Acids
• Oxidation of primary alcohols
• Grignard (GR) synthesis involving carbonation;
• Hydrolysis of nitriles
• Hydrolysis of esters involving saponification;
• Cannizaro reaction
• [X]Synthesis of benzenecarboxylic acids / benzoic acids from
methylbenzene and its derivatives)
Carboxylic Acids from Oxidation of primary
alcohols
• Common oxidizing agents like KMnO4 and K2CrO7 will
oxidize primary alcohols first to aldehyde and further
proceed to yield the carboxylic acid i.e.
• Recall: Trend of oxidation of 10 (primary) alcohols giving
following:
• Primary [10] alcohol [RCH2-OH]  Aldehyde [RCHO] 
carboxylic acid [RCOOH].
• The method can be use in synthesizing both aromatic
and aliphatic carboxylic acids.
Grignard (GR) Synthesis involving
Carbonation;
• Carbon IV oxide (CO2) gas is bubbled into the Grignard reagent, and
on treatment with dilute acid produces the aliphatic acid
• To prepare the aromatic derivative ‘benzoic acid’, the solid carbon IV
oxide (dry ice) react with the aromatic derivative of Grignard reagent,
which also serve to cool the reaction
• Examples
Carboxylic Acids from Hydrolysis of Nitriles:
• 1st is the formation of the nitrile from reaction of
haloalkane with alkali metal cyanide in aqueous alcohol,
which is a solvent that can dissolve both
• Full hydrolysis of the nitrile formed either in alkali give the
carboxylate anion; or the nitrile hydrolysis in mineral acid
produce the free acid
• There is intermediate formation of the amide in both
cases
• Likewise C6H5CN (benzonitrile / benzenecarbonitrile)
hydrolysis to give the benzoic / benzenecarboxylic acid
Carboxylic Acids from Hydrolysis of Esters
Involving Saponification;
• Refluxing esters in concd. NaOH(aq), and treatment in dil. acid yield
carboxylic acid.
Carboxylic Acids from Cannizaro Reaction
• Generally in Cannizaro reaction, an aldehyde that does not have α-
Hydrogens react with concd aqueous NaOH. In this reaction, half the
aldehyde is converted to carboxylic acid and the other half is
converted to an alcohol, hence both oxidation and reduction products
are obtained.
• i.e. When aldehyde reacts with conc. Alkali, it gives both reduction
product (i.e. alcohol) and the oxidation product which is the salt of
the carboxylic acid.
• Aldehydes with no α-H such as methanal/ benzaldehyde undergo self
oxidation and reduction to yield a mixture of an alcohol and a salt of a
carboxylic acid.
 - +
2HCHO 50%NaOH CH 3OH + HCOO Na
methanal methanol Na methanoate

NO 2 CHO 35%NaOH - +
NO 2 CH 2OH + NO 2 COO Na
p-nitrobenzaldehyde Na p-nitrobenzoate
p-nitrobenzylalcohol
{reduction product} {oxidation product}
Reactions of Carboxylic Acids
• Salt formation
• Esterification reactions
• [X]Halogenation
• Conversion to acyl chlorides
• [X]Reduction reactions
• Amide formations
• [X]Decarboxylation of their sodium salts
Salt Formation
• This is an indication of its acidic property
• On reacting with metals carboxylic acids liberate H2
• It gives off CO2 with Na2CO3 or NaHCO3
• With NaOH form the salt and water only
• All above salts can regenerate carboxylic acids by treating them with
dilute mineral acid
Esterification Reactions
• Recall the mechanism of formation of ester and water (only) from
reaction of carboxylic acid with alcohol, involving the alkoxy-hydrogen
fission
C/W:
• Give the names of the esters (and salts) in earlier slides
Conversion to Acyl Chlorides
• These are common reactions of (aromatic and aliphatic) carboxylic
acids, where its hydroxyl group is easily replaced by reacting it with
PCl3 (phosphorus trichloride), PCl5 (phosphorus pentachloride) and
SOCl2 (sulphur dichloride oxide / thionyl chloride) to give the acid
(acyl) chloride
• The reaction with SOCl2 is most appropriate since the other two
products are gaseous and can easily be removed from the mixture.
Amide Formations
• At high temperatures ammonium carboxylates are formed by reacting
carboxylic acid with ammonium carbonate
• The ammonium carboxylate undergo dehydration in the presence of
the free acid to give the amide
• The free acid is important because in its absence the ammonium
carboxylate dissociates on warming.
The 4 Derivatives of Carboxylic Acids
• Derivatives include
Acid chlorides (acyl chloride),
Acid anhydrides,
Esters,
Amides.
• NB: The acyl group [R-C=O] is common to all
On replacing OH of carboxylic acid with
following groups yield
• Following derivatives: [-Cl, -OOCR’, -OR’, -NH2 (or -NHR’, or
-NR’2)]
Acid chlorides (acyl chloride) (-Cl),
Acid anhydrides (-OOCR’),
Esters (-OR’),
Amides [-NH2 (or -NHR’, or -NR’2)]
General Comparison between the Four Derivatives
of Carboxylic Acids
• All four derivatives are polar compounds
• Apart from amides the 1st three (i.e. chlorides, anhydrides and esters) have
normal boiling points similar to those of their aldehydes and ketones with
close relative molecular mass.
• Amides possess some intermolecular H-bonding, hence with fairly higher
boiling points, and do exist as solids. This affords amides to be more
soluble in water than the other derivatives.
• Order of electronegativity of substituent groups thus: -Cl > -OOCR’ > -OR’ >
-NH2;
• Order of reactivity of the acid derivatives: Acid chlorides (acyl chloride) >
Acid anhydrides > Esters > Amides.
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