A. Reaction Mechanisms
1. Free Radical Substitution
Alkanes undergo free radical substitution reaction with chlorine and bromine in the presence
of ultraviolet radiation.
CH4 (g) + Cl2 (g)
CH3Cl (g) + HCl (g)
There are three steps in the mechanism of this reaction, namely initiation, propagation and
termination.
Mechanism
Remarks
INITIATION
Cl2
2Cl
PROPAGATION
CH4 + Cl
CH3 + Cl2
TERMINATION
2Cl
Cl2
CH3 + Cl
CH3 + CH3
CH3 + HCl
CH3Cl + Cl
CH3Cl
CH3CH3
*Note
Homolytic fission
Eg: in free radical reaction
shows the movement of a single
electron
Heterolytic fission
Eg: Breaking of Br2 bond in electrophilic addition
of alkenes
shows the movement of an electron pair
Note: The free radical substitution of alkanes can be controlled by using a large excess of CH4
to yield monosubstituted chloromethane as the major product.
2. Elimination Reaction
Other than cracking, an alkene can be formed by the elimination of a hydrogen halide from a
halogenoalkane or elimination of H2O (dehydration) from an alcohol. Alkyl halides
(halogenoalkanes), RX when heated with alcoholic sodium hydroxide undergo an elimination
reaction. This elimination reaction can occur via two mechanisms, either by a carbocation
intermediate (mainly for 3o alkyl halides (halogenoalkanes)) or a concerted step reaction (mainly
for 1o alkyl halides (halogenoalkanes)).
Via carbocation (E1 Mechanism)
OH
R
H3C
H
R
R
+
H
X
Via a concerted step (E2 Mechanism)
H
C
3.Nucleophilic Substitution
Nucleophilic substitution reactions occur by either SN1 or SN2 mechanism, depending on the
types of halogenoalkanes involved in the reaction.
CH3
slow
Cl
R'
Cl
R'
R"
R"
CH3
Nu-
CH3
Nu
R'
R"
fast
CH3
R'
R"
Nu
Nu
R'
R"
Nu-
Br
Nu
H3C
Br
H
Nu
CH3
H
C
Br
transition state
Energy Profile Diagram
Type of mechanism
SN2
SN2 or SN1
SN1
The inductive and steric effects of substituents can help to explain why primary
halogenoalkane tend to undergo SN2 while tertiary halogenoalkanes tends to undergo SN1
reactions. In both cases it is helpful to consider the intermediate or transition state formed.
Tertiary halogenoalkanes form a more stable/lower energy carbocation ion intermediate in the
SN1 process. The stability of carbocation intermediate depends on the number of R groups
bonded to positively charged (electron deficient) carbon atom.
4
Substitution reactions involving the ionic SN1 mechanism are generally faster than those
proceeding via the SN2 mechanism. Thus the hydrolysis of a tertiary chloroalkane with water
or hydroxide ions is faster than the hydrolysis of a primary chloroalkane under the same
conditions.
CH3
CH3
H3C
C
CH3
Cl
>
H3C
C
H
Cl
H
Cl
>
Cl
>
CH3
B. Chemical Reactions
Alkenes
Reduction (Hydrogenation)
In general, alkenes react with hydrogen gas at high temperature (~150 oC) in the presence of
finely divided heterogeneous nickel catalyst to form the corresponding alkanes.
Example:
Ni
1. CH3CH=CH2 + H2
CH3CH2CH3
heat
Ni
2.
+ H2
heat
Electrophilic Addition
The main chemistry of alkenes revolves around the C=C double bond. The C=C bond is an
electron-rich region with the -electrons susceptible to attack by electrophiles. Alkenes tend
to undergo electrophilic addition reaction which involves the breaking of the -bond and the
two electrons in the -bond are used to form bonds with other atoms.
CH3CH2OH
In the laboratory the same hydration reaction can also take place when an alkene is
mixed with concentrated sulfuric acid followed by heating with water.
H
C C
H H
+ H2O
H2SO4
C C
H OH
H
7
Halogenoalkanes
In halogenoalkane, the carbon (+), which is bonded to the halogen (-), is susceptible to
attack by nucleophiles. Nucleophiles are species (an ion or a molecule) which are strongly
attracted to region of positive charge. Nucleophiles are either negatively charged ions or
neutral molecules with an available lone pair, imparting a strongly - charge on a molecule.
Examples of nucleophiles in the IB syllabus are the hydroxide ion (OH), cyanide ion (CN)
or the ammonia molecule (:NH3). In a nucleophilic substitution reaction, the halogen will be
substituted by the nucleophile.
a) Formation of alcohol
Alcohol is produced when halogenoalkane is warmed with the aqueous hydroxide ion.
Example: In 1-bromopropane, a bromide ion in the halogenoalkane is substituted by
an -OH group to form propan-1-ol.
CH3CH2CH2Br + OH
CH3CH2CH2OH + Br
warm
b) Formation of amine
Amine is produced when halogenoalkane is heated with ammonia in a sealed tube
which serves to prevent the gaseous ammonia from escaping during the reaction.
Example,
CH3CH2CH2Br +
NH3
CH3CH2CH2NH2 + HBr
Heat in
sealed
tube
c) Formation of nitrile
Nitrile is produced when halogenoalkane is heated under reflux with the alcoholic
cyanide ion like alcoholic potassium cyanide.
Example,
CH3CH2CH2Br + CN
Alcoholic
reflux
CH3CH2CH2CN + Br
(one more carbon atom added to chain)
When the nitrile product of the above reaction undergoes reduction, amine is produced.
CH3CH2CH2CN
H2(g)/ Ni(s)
Heat
CH3CH2CH2CH2NH2
CH2
CH2 C
H+
heat
2H2O
H3C
C
CH2
CH2
OH
+ NH4+
Alcohols
Alcohols undergo redox reactions with reactive metals like sodium at room temperature to
form a salt and hydrogen gas. Sodium reacts with ethanol, according to the equation below,
to form sodium ethoxide and hydrogen gas. Effervescence is observed and gas collected will
produce a pop sound with lighted splint.
Example:
2CH3CH2OH (l) + 2Na (s) 2CH3CH2O-Na+ (aq) + H2 (g)
Being a weak acid in nature (weaker than water), alcohols do not react with sodium hydroxide
and sodium carbonate under room temperature.
Oxidation Of Alcohols
Alcohols can be oxidised to form carbonyl compounds or carboxylic acids, depending on the
class of alcohol and the oxidation conditions employed. Generally, primary and secondary
alcohols can be easily oxidised but not tertiary alcohols.
- Primary alcohols are readily oxidised to aldehydes under controlled conditions, the
aldehydes can be further oxidised to form carboxylic acids.
- Secondary alcohols are oxidised to ketones
- Tertiary alcohols do not undergo oxidation.
Ethanol, CH3CH2OH, a primary alcohol, can be oxidised to ethanoic acid. Common oxidising
agents used are acidified aqueous potassium dichromate(VI) or potassium manganate(VII)
solution. The orange dichromate(VI) ion (Cr2O72) is reduced to form the chromium (III) ion
(Cr3+), which is green in colour. Purple manganate (VII) ions will be reduced to form colourless
Mn2+ ions. For oxidation of primary alcohols, strong reaction conditions like refluxing with
strong oxidising agent like MnO4- will favour the formation of the carboxylic acid. Distillation
and the use of a milder oxidising agent like Cr2O72- will favour the formation of aldehyde. The
aldehyde formed must be collected via distillation immediately; otherwise oxidation reaction
will carry on forming carboxylic acid.
Alcohols undergo esterification or condensation reaction with carboxylic acids under reflux
to form sweet-smelling esters. he reaction is slow and reversible, taking hours to reach
equilibrium. The reactant mixture is refluxed and concentrated sulfuric acid catalyst is
added to speed up the reaction. The concentrated sulfuric acid also acts as a dehydrating
agent, removing water from the equilibrium mixture to favour the forward reaction.
O
H3C
CH2
OH
ethanol
C
H3C
OH
ethanoic acid
+ H2O
O
C
H3C
reflux
O
CH2 CH3
H2O
ethyl ethanoate
Carboxylic Acids
Reduction
Carboxylic acids can be reduced by strong reducing agent such as LiAlH4 in ether (as a solvent)
followed by the addition of aqueous acid to products to form primary alcohols. LiAlH4 acts as a
source of hydride ions, H-, a powerful nucleophile (electron pair donor).
(1) LiAlH4/ether
RCOOH
RCH2OH
(2)H2O/H+
Note: H2/Ni cannot be used to reduce carboxylic acids to alcohols. The reduction of a carboxylic
acid to an aldehyde cannot be achieved.
Amines
Reaction of amines with acids (neutralisation)
Amines (and ammonia) act as bases by accepting a proton (H+) from acids. The basic nature of
an amine depends on the availability of its lone pair on the nitrogen atom for accepting a proton
from an acid via dative bond formation.
When primary, secondary or tertiary amines react with acids at room temperature, they are
converted to amine salts. They are named by changing 'amine' to 'ammonium' and by adding
the name of the negative ion (anion).
10
CH3NH3+Cl-
CH3NH2 + HCl
methylammonium chloride
Ammonium salts will yield the free amine when warmed with aqueous sodium hydroxide.
CH3CH2NH3+Cl- (aq)
Amines react with carboxylic acids when heated to form amides that contain the
group.
heat
This condensation reaction is particularly important in biological systems, because amino acids
are bifunctional molecules: they contain both an amine functional group and a carboxylic acid
functional group. There are 20 naturally occurring amino acids that function as the monomers
of proteins in cells.
Eg:
The two amino acids can react (in the presence of enzymes) to form two different condensation
products containing an amide functional group. The amide linkage formed in condensation
reactions of amino acids is also called a peptide bond. It can undergo acid hydrolysis to release
amino acids.
11
C. Isomerism
Isomerism refers to the existence of two or more compounds having the same molecular
formula but different structural formula or different spatial arrangements of atoms. There are
2 main types of isomerism: structural isomerism and stereoisomerism.
Structural Isomerism
Structural Isomerism Compounds having the same molecular formula but different structural
formula. These isomers arise because of the possibility of branching in carbon chains. For
example, there are two isomers of butane, C4H10. In one of them, the carbon atoms lie in a
"straight chain" whereas in the other the chain is branched.
12
b) Positional Isomerism
Compounds having the same molecular formula but different position of a functional group
on a carbon chain or ring
Eg C3H7OH
H H H
H H H
H C C C H
H C C C O H
Eg
H O H
H H H
propan-1-ol
C6H4Cl2
propan-2-ol
Cl
Cl
Cl
Cl
Cl
1,2-dichlorobenzene
1,3-dichlorobenzene
Cl
1,4-dichlorobenzene
13
a) Geometric Isomerism
Recall from hybridisation theory about the restricted rotation about the C=C double bond in
alkenes.
Because of this restriction to rotation, isomers can be formed when there are two non-identical
groups attached to the carbon atoms at each end of the double bond. The smallest alkene
that can show geometric isomerism is but-2-ene.
Sometimes geometric isomerism can result in a marked difference in both chemical and
physical properties in disubstitued cycloalkanes. This tends to occur when there is some sort
of chemical interaction between the substituents. Cis-but-2-ene-1,4-dioic acid melts with
decomposition at 130-131C. However, trans-but-2-ene,1,4-dioic acid does not melt until
286C.
14
In the cis-isomer, the two carboxylic acid groups are closer together so intra-molecular
hydrogen bonding is possible between them. In the trans-isomer, the two carboxylic acid
groups are too far apart to attract each other, resulting in stronger intermolecular forces of
attraction between different molecules and higher melting point. The cis-isomer also reacts
when heated to lose water and form a cyclic acid anhydride. However, the trans-isomer cannot
undergo this reaction.
Consider the compound, 1,2-dichloroethene, ClCH=CHCl. There are two possible
stereoisomers for this compound.
In the cis-isomer, the two Cl-atoms lie on the same side of the C=C bond while in the transisomer, they lie on the opposite sides.
cis-1,2-dichloroethene
trans-1,2-dichloroethene
As a result of geometric isomerism, the physical properties like the melting and boiling points
of the cis-isomer and trans-isomer are different. The cis-isomer of 1,2-dichloroethene has an
overall dipole moment and is polar. However, in the trans-isomer, the two dipole moments
cancel each other and the molecule is non-polar.
cis-1,2-dichloroethene
trans-1,2-dichloroethene
15
By contrast, if we carry out the same transformations on 1,1-dichoroethane, we find that its
mirror image is superimposable on the original.
A chiral molecule does not have a plane of symmetry. Most commonly the molecule contains
a chiral centre: the presence of a carbon atom bonded to four different groups. A plane of
symmetry is defined to be a plane that cuts through the middle of an object (or molecule) so
that one half of the object is a mirror image of the other half. A molecule that has a plane of
symmetry in any of its possible conformations must be identical to its mirror image. For
example, benzene, propanoic acid, CH3CH2CO2H and methylcyclohexane have planes of
symmetry and so they must be achiral.
As enantiomers contain the same groups attached to the same atoms, with the same angles
between each group (unlike geometric isomers), they have exactly the same chemical
properties. They undergo similar chemical reactions, reacting with reagents at identical rates
as long as the reagents are not themselves chiral.
16
Their physical properties density, refractive index, colour, melting and boiling points are
also identical except their effects on plane-polarised light. Enantiomers rotate the plane of
polarised light in opposite directions (but to an equal degree). Plane polarised light differs from
normal light in that electromagnetic waves vibrate in a single plane rather than in multitude of
planes. Passing light through a polariser such as a polarized filter produces polarised light. If
a beam of plane-polarised light is passed through a solution of one enantiomer, when light
emerges, the plane of polarisation is rotated either clockwise or anti-clockwise- this is
measured using a polarimeter. This is the phenomenon of optical activity, and is the reason
they are called optical isomers.
If we have a solution that contained equal concentrations of the two enantiomers, the
clockwise rotation caused by one enantiomer will be exactly cancelled by the anticlockwise
rotation caused by the other enantiomer, resulting in zero net rotation. This equimolar mixture
of two enantiomers is called the racemic mixture, and is usually formed when a chiral
compound is synthesised from non-chiral starting materials.
17
D. Polymerisation
Addition Polymerisation
Polymerisation is the chemical process where smaller molecules (monomers) react to form
chemical bonds to form macromolecules (polymers). Typically a polymer molecule is made up
of 104-106 monomers.
There are mainly two types of polymerisation process: addition polymerisation and
condensation polymerisation.
Alkenes or substituted alkenes tend to undergo addition polymerisation.
Addition polymerisation is an important process where plastics are formed. Some common
addition polymers are shown in the table below.
Polymer / Common
name
Polyethene or
polyethylene, PE
Monomer
General Formula
Ethene,
H
H
C
Chloroethene,
Cl
F
C
H
C
Styrene,
H
C
H
lab equipments,
automobile parts
n
CH3
Propene,
plastic pipes,
artificial leather,
wire insulation
Tetrafluoroethene,
plastic bottles,
toys, plastic bags,
film wrap
n
H
Cl
Polystyrene, PS
Polypropene, PP
Polytetrafluoroethene,
PTFE
Polychloroethene or
polyvinyl chloride, PVC
Uses
CH3
foamed packaging,
disposable cups
and plates
18
conc H2SO4
RCOOR
reflux
+ H2O
If two functional groups are present in the molecules, it will be possible to form a condensation
polymer.
The most widely used condensation polymers are polyesters and polyamides. Polyesters are
useful for forming fibres for making clothes, for example, it has been used extensively in the
production of trousers and skirts. Polyesters can also be used for packaging films. In addition
a polyester resin polyethylene terephthalate (PET) has low permeability to carbon dioxide and
so is used extensively in the bottling of carbonated drinks.
19
Because the two monomers each contain a six-carbon chain, this form of nylon is known as
nylon-6,6. The commercial formation of nylon-6,6 requires high temperature, high pressure
and presence of catalyst.
The molecular chains of nylon fibres interact by hydrogen bonding between the hydrogen
atoms of N-H groups of the amide linkage of one polymer chain with the >C=O groups on the
adjacent polymer chain.
Nylons are used in engineering applications and in making fibres. A combination of strength
and resistant to abrasion makes nylon good for making bearings and gears. As a fibre, nylon
is used to make clothing to mountaineering ropes.
20
E. Physical Properties
A homologous series is a series of organic compounds that have the same functional groups
but differ in formula by a fixed group of atoms. In the example below, each alkane differs from
the next in the series by a -CH2- unit.
Members of a homologous series have similar chemical properties and they may be prepared
by the same methods. However, they have different physical properties eg. melting points and
density. As the chain length (numbers of carbons) increases, the melting and boiling points of
the homolog gradually increases. The longer chain molecules have higher boiling points as
they have greater intermolecular forces (van Der Waalss forces).Branching present within
the molecule will lower its boiling point. Branched molecules are more compact and
have a smaller surface area for Van der Waals forces of attraction to operate. Thus,
less thermal energy is required to overcome the weaker intermolecular forces.
The physical properties of alkenes are quite similar to alkanes.Some key physical properties.
The melting point and boiling point of alkenes increases with increasing size of electron
cloud. Example: ethene, propene and butene are gases at r.t.p. while the rest of the
alkenes are liquids or solids.
Due to geometric isomerism in some alkenes which results in difference in the overall
polarity of the molecule, the melting and boiling points of a pair of geometric isomers
may be different.
All alkenes are insoluble in water due to lack of favourable interactions with water
molecules.
Halogens are more electronegative than carbon. The carbon-halogen bond will be polarised
with the partial positive charge residing on the carbon atom as shown below. The polarisation
of the carbon-halogen -bond is most pronounced in the C-F bond and the least in the C-I
bond. Halogenoalkanes are usually polar molecules as the dipole moments do not cancel out
(except in some like CCl4). Despite being polar molecules, halogenoalkanes are generally
insoluble in water except for the short chain fluoroalkanes.
X= F, Cl, Br or I
21
Halogen
F
Cl
Br
195
235
276
306
249
285
320
351
277
312
344
374
316
345
376
403
Parent alkane
methane
ethane
propane
butane
Increasing
Boiling
Point
(in K)
Alcohols have much higher boiling points compared to alkanes of similar Mr.
CH3CH2CH2CH2CH3
CH3CH2OCH2CH3
CH3CH2CH2CH2OH
Mr
72
74
74
bp oC
36
35
117
The much higher boiling point of alcohol is due to the stronger intermolecular hydrogen bonds
in alcohols compared to the weak intermolecular van der Waals forces in alkanes.
Branched alcohols have lower boiling points compared to straight-chain isomers as a highly
branched isomer has a lower surface area. Hence the extent of intermolecular Van der Waals
forces of attraction is smaller for branched isomers, resulting in the lower boiling points.
(CH3)3COH
CH3CH2CH2CH2OH
Mr
74
74
Bpt oC
82
117
Phenols exist as crystalline solids with low melting point of 34C. As a liquid, phenol has
relatively high boiling point as compared to other organic compounds (e.g. alkanes) of the
same molecular mass. This is because a large amount of thermal energy is needed to
overcome strong hydrogen bonds between phenol molecules
Similar to water, the oxygen atom on the hydroxyl group has two lone pairs which are capable
of forming hydrogen bonds with water molecules. However, the extent of solubility of alcohols
in water is dependent on the chain length of the alkyl group. Alcohols up to three carbons long
are completely miscible with water. Alcohols with four carbons or more are partially miscible
or immiscible with water due to their lower polarity.
22
Phenols are usually insoluble in water due to the large hydrophobic phenyl group
Carboxylic acids have higher boiling points than most organic compounds of similar Mr as
they are able to form strong intermolecular hydrogen bonds. More thermal energy is required to
overcome the stronger hydrogen bonds than permanent dipole-permanent dipole interactions
and van der Waals forces.
Carboxylic acids have higher boiling points than alcohols of similar Mr. This is due to the stronger
hydrogen bonding found in carboxylic acids due to the presence of the electron-withdrawing
carbonyl group.
e.g.
CH3COOH
bp = 118 oC
Mr = 60
CH3CH2CH2OH
bp = 97 oC
Mr = 60
Carboxylic acid molecules can also pair off to form dimers via intermolecular hydrogen bonds,
a dimer consists of two identical molecules interacting together:
Structure of a dimer:
Carboxylic acids with four carbon atoms or less are soluble in water due to the formation
hydrogen bonds with water molecules. Water solubility decreases (since molecular polarity
decreases) as the carbon chain (alkyl) length of the carboxylic acid increases.
Esters cannot form hydrogen bonds with one another as no hydrogen is attached directly to
oxygen of the ester group. Esters are polar in nature; their molecules are held together by
permanent dipole- permanent dipole interactions. They have higher boiling points than non polar
hydrocarbons but lower boiling points than carboxylic acids and alcohols of similar molecular
mass.
23
Amides are neutral molecules. Amides (except for those with no hydrogen atom attached to
nitrogen) form strong intermolecular hydrogen bonds. Consequently, such amides have high
boiling points. Their boiling points are even higher than those of carboxylic acids of
comparable molar mass.
For example, the boiling point of methanamide is 210 C while the boiling point of methanoic
acid is 101 C. Methanamides ability to form an extensive network of hydrogen bonds
accounts for its high boiling point:
24
F. NOMENCLATURE
Displayed/
Full Structural
Examples:
Formula
3D Full Structural
Formula
Condensed/
structural
formula
Skeletal
structure
Displayed formula or full structural formula is a more complete way of showing which atoms
are bonded to which and it also shows ALL the type of bonds (e.g single, double) present in
the molecule.
In condensed formulae, all the bonds are removed. Brackets e.g. (CH3), (OH) are introduced
to signify a branch in the main chain. When interpreting condensed formula, take note that
each carbon atom should have four bonds (whether single, double or triple). Usually, CO refers
to the carbonyl group C=O and CHO refers to the aldehyde functional group
IUPAC system of nomenclature is to establish an international standard of naming compounds
to facilitate communication. The goal of the system is to give each structure a unique and
unambiguous name, and to correlate each name with a unique and unambiguous structure.
IUPAC nomenclature is based on naming a molecules longest chain of carbons that includes
the functional group. All deviations, either multiple bonds or substituent atoms other than
carbon and hydrogen, are indicated by prefixes or suffixes according to a specific set of
priorities.
The name of an organic molecule is made up of 3 parts: the Prefix, the Stem and the Suffix.
The stem part of the name refers to the longest possible continuous carbon chain that includes
the functional group*, if there are any. Referring to the table below, functional groups of
highest priority is indicated by suffix; the others are indicated by prefix. Functional groups are
organised below in order of increasing priority.
25
Steps to naming:
5-chlorohex-2-ene
2,3-dimethylpentane
3-methylbutan-2-ol
3-bromobutanoic acid
26
H3C
CH3
CH3
N,N-dimethylethanamide
Eg.
methanamide
ethanamide
2-methylpropanamide
Amines
Amines are classified into primary, secondary and tertiary amines, according to the number of
hydrogen atoms replaced by alkyl (R) or aryl (Ar) groups.
R-NH2
R-N-R'
|
H
R-N-R'
Tertiary amines (3o) have 3 hydrogen atoms being replaced.
|
R"
Primary amines are named with the NH2 group as the prefix - amino. For secondary and
tertiary amines, the alkane name is used for the longest amine chain but replace -e with-amine.
More complex names are the amines that have one or two alkyl groups attached to the
nitrogen atom in place of hydrogen atoms. In such cases, continue the naming process by
naming the alkyl groups as attachments to the front of the name using N- to show their location.
Eg:
H
H C
H
H
C
H
H
C
H
H
N
H
C H
H
N-methylpropanamine
The alkyl groups attached to the nitrogen atom are named in alphabetical order, prefixes like 'di'
or 'tri' are used for naming identical alkyl groups.
27
IUPAC Name
CH3CH2CH2NH2
propanamine/ 1-aminopropane
CH3-CH-CH2CH3
|
NH2
2-aminobutane
ClCH2CH2NH2
2-chloroethanamine/ 1-amino-2chloroethane
NH2
phenylamine/aniline
CH3CH2-N-CH2CH3
|
CH2CH3
N,N-diethylethanamine
CH3-CH2-CH2-CH2-N-CH2-CH3
|
CH3
N-ethyl-N-methylbutanamine
Nitriles
In naming nitrile, select the longest carbon chain starting with the carbon in the nitrile group.
Then use the alkane name for that chain and add in the word nitrile.
Esters
In naming esters, name the alcohol part first then the acid part, replacing oic acid with oate.
For example, CH3CH2COOH is propanoic acid, and CH3CH2COO is the propanoate group.
The acid is named by counting up the total number of carbon atoms in the chain - including
the one in the -COOH group.
Carboxylic Acids
The longest continuous carbon chain containing the carboxyl group is selected as the suffix.
Replace the terminal 'e' from the corresponding hydrocarbon name with oic acid.
28
HCOOH
methanoic acid
CH3COOH
ethanoic acid
For substituted acids, the parent chain is numbered beginning with the carboxyl group.
When a compound contains both a carboxyl group and a hydroxyl group, the hydroxyl group
has a lower priority. The hydroxyl group is treated as a prefix and is named as hydroxy.
H3C
CH3
HO
Eg:
O
C
OH
CH3
3-hydroxy-2,2-dimethylbutanoic acid
Carboxylic acids containing 2 carboxyl (-COOH) groups are named as a dioic acid.
Eg:
HOOCCH2COOH
1,3-propanedioic acid
The simplest aromatic acid is benzoic acid (benzene carboxylic acid); other substituents are
named as derivatives of benzoic acid.
Alkenes
Similar to alkanes, the alkene parent chain is the longest continuous carbon chain that
contains the C=C bond. The position of the C=C bond is given priority in numbering and is
indicated by the smaller of the two number labelling the carbon atoms.
Example
but-1-ene
CH3
CH3
CH3
CH3
CH3
3,3-dimethylbut-1-ene
CH3
1,3,3-trimethylcyclohexene
CH3
CH2
H3C
CH3
C
H
C
CH3
CH3
29
R
R
X
0
primary
No R groups
X
0
1
primary
2
secondary
1 R group
2 R groups
30
tertiary
3 R groups
The naming of the halogenoalkanes is similar to that of alkanes with the addition of a prefix to
indicate the position of the carbon atom to which the halogen is attached to. The numbering
of the carbon should be the smallest possible. If there is more than one type of halogen, the
order of naming will follow the alphabetical order.
Examples
H H H
H H H H
Cl
C C
C C
2-iodobutane
2-iodobutane
chlorobutane
1-chlorobutane
Cl H H H
H C C C C
H
H H H H
H C C
C C C H
H Br H H H
2-bromo,1-chloropentane
2-bromo-1-chlorobutane
Cl F
H H
H C C C C
H Cl H H
1,2-dichloro,
2-fluorobutane
1,2-dichloro-2-fluorobutane
30