3.

1 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

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

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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

Prefix* H H H
Halogenoalkanes chloro- 1-chloropropane
C halogen H C C C Cl
bromo-
iodo- H H H Cl

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

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

suffix* -oic acid

Carboxylic acids O H O O ethanoic acid
C OH H C C OH

H
OH
-yl –oate
O
H O H O methylethanoate
Esters C O
H C C O C H

H H
O

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 (and the lowest number on the carbon
chain), 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 >aldehydes>ketones>alcohols>alkenes>halogenoalkanes

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 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.

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 prefixes -fluoro, -chloro, -bromo, or –iodo. (Give the
position number if necessary) H H H H
I
Cl

Br
Cl
F
Br
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 carbon 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 hydroxy 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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 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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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

position 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
H H
H H Note: alkene and cyclo alkanes have the same general formula. Hexene and
cyclohexane have the same molecular formula but have a different functional
group

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Stereoisomerism

Stereoisomers have the same structural formulae but Alkenes can exhibit a type of isomerism
have a different spatial arrangement of atoms. called E-Z stereoisomerism

E-Z isomers exist due to restricted E-Z stereoisomers arise when:

rotation about the C=C bond (a) There is restricted rotation around the C=C double bond.
(b) There are two different groups/atoms attached both ends of the
Single carbon-carbon covalent double bond.
bonds can easily rotate
But-1-ene is a structural isomer of But-2-ene
H H but does not show E-Z 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 EZ isomers
C C
H H H H H H
H
Z- but-2-ene H two identical groups attached to one
end of the restricted double bond –
H no E-Z 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 Z-but-2-ene
H C switched to the other.
H
H
E-but-2-ene
E -but-2-ene

Naming E-Z stereoisomers Priority Group: The atom with the bigger
First determine the priority groups on both sides of the double bond atomic number is classed as the priority atom
Priority Priority
group Cl Cl group Cl H
side 1 side 2
C C C C
Z-1,2-dichloroethene
H H H Cl E-1,2-dichloroethene
If the priority atom is on the same side of the
If the priority atom is on the opposite side of the
double bond it is labelled Z from the german
double bond it is labelled E from the german
zusammen (The Zame Zide!)
entgegen (The Epposite side!)

Cahn–Ingold–Prelog (CIP) priority rules.

1. Compare the atomic number of the

atoms directly attached to each side of the priority Cl Br
priority
double bond; the atom of higher atomic
number is given priority. C C

2. If the atoms are the same, consider the

atoms at distance 2 from the double bond.
H Cl
Make a list of each atom bonded to the one
directly attached to the double bond. H3C
Arrange list in order of decreasing atomic
CH3
priority
number. Compare the lists atom by atom; at
the earliest difference, the group containing priority
C C
the atom of higher atomic number is given CH2 H
priority
H3C
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The effect of EZ stereoisomerism on physical properties
E-Z stereoisomers can have differing melting and boiling points.
δ- δ-
Cl δ- Cl Cl H

δ+ C C δ+ δ+ C C δ+

H H H Cl δ-
Z-1,2-dichloroethene
Boiling point =60oC E-1,2-dichloroethene
This molecule is polar. The polar C-Cl bonds are on Boiling point =48oC
the same side of the molecule. One side of the This molecule is non- polar. The polar C-Cl
molecule is slightly negative. bonds are on opposite sides of the molecule.
The intermolecular forces are both van der waals The dipoles cancel out.
and permanent dipole-dipole attractions. The intermolecular forces are only van der
waals so lower boiling point.

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