14 Organic: Basic Concepts

Basic definitions
Hydrocarbon is a compound consisting of hydrogen and carbon only to know

Saturated: Contain single carbon-carbon bonds only Unsaturated : Contains a C=C double bond

Molecular formula: The formula which shows the actual number of each type of atom

Empirical formula: shows the simplest whole number ratio of atoms of each element in the compound

General formula: algebraic formula for a homologous series e.g. CnH2n

Structural formula shows the minimal detail that shows the arrangement of atoms in a
molecule, eg for butane: CH3CH2CH2CH3 or CH3(CH2)2CH3,

Displayed formula: show all the covalent bonds and atoms present in a molecule

Drawing Displayed formulae Remember that the shape around the

carbon atom in saturated hydrocarbons is
H H H H tetrahedral and the bond angle is 109.5o
When drawing organic
H C C C C H compounds add the
hydrogen atoms so that H H
H H H
H C H each carbon has 4 bonds
H C C H
H

H H

Skeletal formula shows the simplified organic formula, shown by removing hydrogen atoms from alkyl chains,
leaving just a carbon skeleton and associated functional Groups.

OH

But-2-ene Butan-1-ol
2-methylbutane cyclohexane cyclohexene

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Functional group is an atom or group of atoms which when present in different molecules
causes them to have similar chemical properties

Homologous series are families of organic compounds with the same functional
group and same general formula.
•They show a gradual change in physical properties (e.g. boiling point).
• Each member differs by CH2 from the last.
• same chemical properties.

prefix / suffix
homologous functional example
(* = usual use)
series group
Alkane
C C CH3CH2CH2CH3
-ane Butane

H H
Alkenes C C suffix -ene C C propene
H
H C
H
H

suffix* -ol H H H Propan-1-ol

Alcohols prefix hydroxy-
C OH H C C C O H
OH
H H H

H H H
Halogenoalkanes prefix chloro-
1-chloropropane
halogen H C C C Cl
C
bromo- Cl
H H H
iodo-

suffix -al H O
Aldehydes O
prefix formyl- H C C H
O ethanal
C H
H

suffix* -one H O H
O O Propanone
prefix oxo-
H C C C H
Ketones C
H H

suffix -oic acid

carboxylic acids H O O Ethanoic acid
O
H C C OH
C OH
H
OH
-yl –oate
O
methylethanoate
Esters C O H O H O
H C C O C H

H H
O

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 prefix / suffix
homologous functional group example
(* = usual use)
series
suffix -nitrile H H
nitriles
C N prefix cyano- H C C C N Propanenitrile
H H
suffix* -amine
amines C NH2 prefix amino-
H H H
Propylamine
H C C C NH2
Or propan-1-amine
H H H
O
O
Acyl chloride
C -oyl chloride CH 3 C ethanoylchloride
Cl
Cl

O O
Amide
C -amide CH3 C ethanamide
NH2
NH2

General rules for naming carbon chains no of

code
carbons
Count the longest carbon chain and name appropriately
meth 1
Find any branched chains and count how many carbons they contain
eth 2
 Add the appropriate prefix for each branch chain
prop 3
Eg -CH3 methyl or -C2H5 ethyl –C3H7 propyl
1 CH but 4
3
pent 5
2 CH2 hex 6
5 3,5-dimethylheptane
hept 7
H3 C CH CH2 CH CH3
3 oct 8
4
CH2 6 non 9

dec 10
CH3 7

Basic rules for naming functional groups

The functional group is named by a prefix or suffix. e.g. bromoethane, ethanol, propene

•When using a suffix, add in the following way :

If the suffix starts with a vowel- remove the –e from the stem alkane name
e.g. Propan-1-ol, butan-1-amine, ethanoic acid, ethanoylchloride, butanamide

If the suffix starts with a consonant or there are two or more of a functional group meaning di, or tri needs to be
used then do not remove the the –e from the stem alkane name
e.g. Propanenitrile, ethane-1,2-diol, propanedioic acid, propane-1,2,3-triol, Pentane-2,4-dione.

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 When compounds contain more than one functional group, the order of precedence determines which groups are
named with prefix or suffix forms. The highest precedence group takes the suffix, with all others taking the prefix
form. However, double and triple C-C bonds only take suffix form.
Order of priority highest first:
Carboxylic acids >carboxylic acid derivative>nitriles>aldehydes>ketones>alcohols>amines>alkenes>halogenoalkanes

The position of the functional group on the carbon H H H O H

chain is given by a number – counting from the end
H C C 3 C2 C1 H Butan-1-ol
of the molecule that gives the functional group the 4
lowest number. For aldehydes, carboxylic acids &
H H H H
nitriles, the functional group is always on carbon 1.
H H H

We only include numbers, H C C C H

methylpropane CHCl3 trichloromethane
however, if they are needed H H
to avoid ambiguity. H C H

•The functional groups take precedence over branched 3-methylbut-1-ene is correct and not 2-methylbut-3-
chains in giving the lowest number ene
H H H H H

Where there are two or more of the same groups, di-, tri- , H C C C C C H 2,3-dibromopentane.
tetra-, penta- or hexa- are used. Note the point made above
H H Br H
about the addition of ‘e’ to the stem Br

Words are separated by numbers with dashes CH2FCCl2CH2CH3 2,2-dichloro-1-fluorobutane.

 numbers are separated by commas
CH2FCH2CHBrCH2CH3 3-bromo-1-fluoropentane
If there is more than one functional group or side chain, the
groups are listed in alphabetical order (ignoring any di, tri).

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Alkenes
2 4
1 3 Double bond between
The double bond will be between two carbons. Use the lower
C2 and C3 so But-2-ene
number of the two to show the position of the double bond

The name for alkenes may include E or Z at start to show Z-but-2-ene

the type of stereoisomer

If more than one double bond is present then suffix Penta-1,3-diene

ends diene or triene. The stem ends in a
The suffix -en for alkenes can go in front of other suffixes. CH2OHCHBrCH=CH2 2-bromobut-3-en-1-ol
The alcohol and carboxylic acid groups have higher priority OH
than the alkene group so take precedence with numbering
E-but-2-enoic acid
O

Halogenoalkanes H H Br H
Class the halogen as a substituent on the C chain and use 2-bromobutane
H C C C C H
the suffix -fluoro, -chloro, -bromo, or –iodo. (Give the
position number if necessary) H H H H
I

Cl
Br
Cl Br
F
2,3-dichloro-1-fluoro-3-methylpentane 5,5-dibromo-4-iodo-3-methylpent-1-ene

Multiple functional group and side chains are listed The alkene group has higher priority than the
in alphabetical order (ignoring any di, tri). halogenoalkane group so it takes the lowest number
on the carbon chain

Alcohols
These have the ending -ol and if necessary the position OH

number for the OH group is added between the name Butan-2-ol

CH3 CH CH2 CH3
stem and the –ol 1 2 3 4

If there are two or more -OH groups then di, tri are HO CH2 CH2 OH Ethane-1,2-diol
used.
Add the ‘e’ on to the stem name though. H2C CH CH2 propane-1,2,3-triol
OH OH OH
Cl
The OH group has a higher priority than the
halogenoalkane group and alkene so takes
precedence in numbering. The OH is on carbon 1 OH
Cl
E-3,6-dichlorohex-4-en-1-ol
O
If the compound has an –OH group in addition to another
H3C CH C 2-hydroxypropanoic acid
functional group with a higher priority. The priority group gets
the suffix ending and the OH can be named with the prefix OH OH
hydroxy-:

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 H
Aldehydes O

An aldehyde’s name ends in –al

It always has the C=O bond on the first carbon of H C C

the chain so it does not need an extra number. It is

by default number one on the chain. H
H

Ethanal

If two aldehyde groups then di is put before –al and an O O

e is added to the stem.
pentanedial

O
Aldehydes have a higher priority than alcohol so the –OH HO
group uses the hydoxy prefix. 4-hydroxybutanal

Ketones H O H

Ketones end in -one H C C C H

When ketones have 5C’s or more in a chain then H H

it needs a number to show the position of the Propanone
double bond. E.g. pentan-2-one
H O H O H
If two ketone groups then di is put before – H C C C C C H
one and an e is added to the stem.
H H H
Pentane-2,4-dione

Carboxylic acids H H
O
These have the ending -oic acid but no number is
necessary for the acid group as it must always be H C C C Propanoic acid
at the end of the chain. The numbering always
starts from the carboxylic acid end. H H
O H

O O Ethanedioic acid
If there are carboxylic acid groups on both ends of the
C C
chain then it is called a - dioic acid Note the e in this name
HO OH

O
5-hydroxy-4-methylpentanoic acid

OH OH

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Amines H H H
H2N O
These end in –amine.
There is, however, rather confusingly two H C C C NH2 If there is another priority
functional group as well CH C
ways of using this suffix.
H H H as the amine group then
The exam board tend to use the common
version where the name stem ends in -yl propylamine the prefix amino is used. H 3C O H

propylamine. Or propan-1-amine 2-aminopropanoic acid.

The IUPAC version of the same chemical
is propan-1-amine. (This is used in the
same way as naming alcohols)

If there are two amine groups then name H H It could also be named
as following N (CH2)6 N 1,6-diaminohexane
H H
hexane-1,6-diamine

If amine groups are attached to a NH2

benzene ring then name as following
phenylamine

H H H OH
Nitriles
H3C
These end in –nitrile, but the C of the C
H C C C CN
CN group counts as the first carbon of C
the chain. Note the stem of the name is H3C N
H H H
different : butanenitrile and not
butannitrile. 2-hydroxy-2-methylpropanenitrile
butanenitrile

Carboxylic acid derivatives

Esters
H H O H
Esters have two parts to their names
The bit ending in –yl comes from the alcohol that has formed it H C C C O C H
and is next to the single bonded oxygen.
The bit ending in –anoate comes from the carboxylic acid. H H H
(This is the chain including the C=O bond) methylpropanoate

Acyl Chlorides
O H3C O
O O
add –oyl chloride to the stem CH3 C CH C
name
C (CH2)3 C
Cl H3C Cl
Cl Cl
ethanoyl chloride 2-methylpropanoyl chloride Pentanedioyl dichloride

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 Amides
O Secondary and tertiary amides are
Add –amide to the stem named differently to show the two O
name CH3 C (or three) carbon chains.
NH2 The smaller alkyl group is preceded
by an –N which plays the same role H3C CH2 C NH CH3
ethanamide as a number in positioning a side
N-methylpropanamide
alkyl chain

O CH3
CH3 O CH3
H3C CH2 C N CH3
H3C CH C N CH3
N,N-dimethylpropanamide N,N,2-trimethylpropanamide

Naming aromatic molecules

Naming aromatic compounds can be complicated. The simplest molecules are derivatives of benzene and have benzene
at the root of the name

CH3 C2H5 Cl Br NO2 CO2H CHO

Methylbenzene ethylbenzene chlorobenzene bromobenzene nitrobenzene benzenecarboxylic acid benzaldehyde

If two or more substituents are present on the benzene ring, their positions must be indicated by the use of numbers.
This should be done to give the lowest possible numbers to the substituents. When two or more different substituents
are present, they are listed in alphabetical order and di, tri prefixes should be used.

CH3 COOH CH3

CH3 O 2N NO2

CH3
Cl OH NO2
1,3-dimethylbenzene
1-chloro- 4-methylbenzene 4-hydroxybenzenecarboxylic acid 2,4,6-trinitromethylbenzene

In other molecules the benzene ring can be regarded as a substituent side group on another molecule, like alkyl groups
are. The C6H5- group is known as the phenyl group.

O
NH2 CH CH2 CH3
H3C CH CH2 CH3 O
C
H3C C O

phenylamine phenylethene
2-phenylbutane
phenylethanone phenylethanoate

OH

OH

1-phenylpropane-1,2-diol 3-phenylpropanal

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Shapes of organic molecules; σ and π bonds

Ethane C2H6
H H
Each carbon in ethane has four σ
bonds. They are arranged in a This is the shape and bond angle
C C
H H of any saturated hydrocarbon
tetrahedral way around the
carbon. The bond angle is 109.5o
H
H

Ethene C2H4
Each carbon in ethene forms two H H
σ bonds to hydrogens. The arrangement of bonds
C C
C=C double covalent bond around the >C=C< is
consists of one sigma (σ) bond H H planar and each bond has
and one pi (π) bond. the bond angle 120o

Carbonyls also have the same

planar arrangement of bonds with
a 120o bond angle

Benzene’s Structure Benzene is a planar molecule. The

The simplest arene is benzene. It has the molecular formula C6H6 evidence suggests all the C-C bonds are
Its basic structure is six C atoms in a hexagonal ring, with one H atom the same and have a length and bond
bonded to each C atom. energy between a C-C single and C=C
Each C atom is bonded to two other C atoms and one H atom by single double bond.
covalent σ-bonds. This leaves one unused electron on each C atom in a p
orbital, perpendicular to the plane of the ring. In formulae we draw a circle to show this
The Six p electrons are delocalised in a ring structure above and below delocalised system.
the plane of carbon atoms.

H H H H

H H H H Abbreviated
formula
H H H H
Displayed formula

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Isomers
Structural isomers: same molecular formula different structures (or structural formulae)

Structural isomerism can arise from

•Chain isomerism
•Position isomerism
•Functional group isomerism

Chain isomers: Compounds with the same molecular formula but different
structures of the carbon skeleton
H
H H H H H H H H H
H C H
H C C C C H H H
H C C C C C H
H C C C H
H H H
H H H H H H C H H H
H C H
pentane H
H
2-methylbutane
2,2-dimethylpropane

positional isomers: Compounds with the same molecular formula but different structures due to
different positions of the same functional group on the same carbon skeleton

H H H H H H

H C C C H 1-bromopropane H C C C H 2-bromopropane

Br H H H Br H

Functional group isomers: Compounds with the same molecular formula but with
atoms arranged to give different functional groups

H H H H
Methoxymethane: an ether
H C C O H ethanol: an alcohol H C O C H

H H
H H

H H
H H
C
H C C H
Cyclohexane- cyclo alkane CH3CH2CH2CH2CH=CH2 hexene- alkene
H C C H
C Note: alkene and cyclo alkanes have the same general formula. Hexene and
H H
H H
cyclohexane have the same molecular formula but have a different functional
group

Aldehydes and ketones of the same chain length would be classed as functional
group isomers- e.g. Propanal and propanone (both C3H6O)

Questions often involve functional group isomers of carboxylic acids: including esters etc
H 3C CH2 O O O OH OH OH
CH 2 C H 3C C O CH 2 CH 3 H 3C C CH 2 CH 2 H 2C CH CH CH 2
OH

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Stereoisomerism
Stereoisomers have the same structural formulae but have a different spatial arrangement of atoms.

Geometrical (cis-trans) isomerism

Alkenes can exhibit a type of isomerism called Geometrical (cis-trans) isomerism

Geometrical (cis-trans) isomers exist due Geometrical (cis-trans) arise when:

to restricted rotation about the C=C (a) There is restricted rotation around the C=C double bond.
bond due to the presence of π bonds (b) There are two different groups/atoms attached both ends of the
double bond.
Single carbon-carbon covalent
bonds can easily rotate
But-1-ene is a structural isomer of But-2-ene
H H but does not show cis-trans isomerism.
two different groups H H
H C C H attached either end of the
restricted double bond- H C C H But-1-ene
C C
leads to geometrical (cis-
H H H H trans) C C
H H
H
cis- but-2-ene H two identical groups attached to one
end of the restricted double bond –
H no cis-trans isomers
H
These are two isomers as
C H
the lack of rotation Skeletal formulae can also represent E-Z isomerism
H
C C around the double bonds
H means one cannot be cis-but-2-ene
H C switched to the other.
H
H
trans-but-2-ene
trans -but-2-ene

Optical Isomerism

The second type of stereoisomerism: is optical isomerism

Optical isomerism occurs in carbon compounds with 4 A carbon atom that has four
different groups of atoms attached to a carbon (called an H H H H
different groups attached is
asymmetric carbon). called a chiral (asymmetric)
H C C C C H
carbon atom
H H O H
These four groups are arranged
tetrahedrally around the carbon. H

OH OH This causes two different

isomers that are not
Many naturally occurring molecules
C C superimposable to be
contain chiral C atoms, but are usually
CH3 H3C C2 H5 formed. They are mirror
H5 C2 found in nature as a pure enantiomer
H H images

Two compounds that are optical isomers of Optical isomers have similar physical and chemical properties, but
each other are called enantiomers. they rotate plane polarised light in different directions.

One enantiomer rotates it in one direction and the other enantiomer

rotates it by the same amount in the opposite direction.

One optical isomer will rotate light clockwise (+)(called

dextrorotatory). The other will rotate it anticlockwise(-)(called -ve enantiomer +ve enantiomer
Anticlockwise clockwise rotation
laevorotatory).
rotation

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 Introduction to Mechanisms
To understand how the reaction proceeds we must first understand how bonds are broken in organic mechanisms
There are two ways to break a covalent bond:
1.HOMOLYTIC FISSION:
each atom gets one electron from the covalent bond
one headed arrow shows
movement of one electron
Y X Y
X

The bond has broken in a process called homolytic fission.

When a bond breaks by homolytic fission it forms two Free Radicals. DEFINITION

Free Radicals do not have a charge and are represented by a A Free Radical is a reactive species
which possess an unpaired electron
2. HETEROLYTIC FISSION: (one atom gets both electrons)

X Y X: - Y+
two headed arrow shows
movement of pair of
OR - electrons
X Y X+ Y:

+ -
xx xx

xx
xx

Cl Cl Cl + Cl
x

xx xx

Heterolytic fission produces IONS

Most organic reactions occur via heterolytic fission, producing ions

The Mechanism: To understand a reaction fully we must look in detail at how it proceeds step
by step. This is called its mechanism
A curly arrow will always
We use curly arrows in mechanisms to show the movement of an electron
start from a lone pair of
pair showing either breaking or formation of a covalent bond;
electrons or the centre
of a bond

The formation of a covalent The breaking of a covalent bond

bond is shown by a curly is shown by a curly arrow starting
arrow that starts from a lone from the bond.
electron pair or from HO:-
another covalent bond
H H H H

H C C δ+ X δ- H C C OH + X-

H H
H H

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