Structure and Formulae

Mod. 1 1.
Objectives
• explain the occurrence of carbon compounds with straight chains, branched chains and rings
• explain the meaning of the term ‘homologous series’
• distinguish among empirical, molecular, and structural formulae
• determine formulae from experimental data
• write structural formulae: Displayed, Condensed
• apply the IUPAC rules to named organic compounds
• define, structural isomerism
• explain stereoisomerism
• determine the possible isomers from given molecular formulae
Which of these would be considered organic?
Intro to carbon compounds
• Organic chemistry is the study of compounds of carbon

• Living organisms, to a large extent, consist of carbon-based

compounds and also produce many other organic compounds,
some of which are very useful to us
• An enormous number of carbon compounds, probably about
20 million, have already been described. No other element
comes close to matching this
Bonding in carbon compounds

• Carbon is tetravalent – has 4 valence electrons that are available for

covalent bonding

• For example, in methane the tetravalent carbon atom can form a strong covalent bond with each of four
hydrogen atoms
Bonding in carbon compounds
• Carbon has the ability to bond with other carbon atoms to form straight chains,
branched chains and ring compounds of varying lengths
• This property is called catenation

• C-C bonds are fairly strong, requiring a lot of energy to break, making their
compounds stable
Bonding in carbon compounds
• Carbon has the ability to mix and rearrange the four orbitals in the outer shell
• This property is called hybridization
Bonding in carbon compounds

• All three types of bonding pattern are

very strong and allow the formation
of stable organic compounds
Bonding in carbon compounds
• Sp3 Hybridization (Methane)
• Sp2 Hybridization (Ethene)

• Sp3 Hybridization (Ethane)

Bonding in carbon compounds
• Carbon compounds can display resonance
• Molecular orbitals extend over more than 2 atoms
• Electrons become delocalized within the molecule contributing to increased stability

• For example, Benzene is an extremely stable

molecule due to its geometry and molecular
orbital interactions, but most importantly, due to
its resonance structures
• The bonds between the C atoms are neither single
or double bonds but somewhere in between
• The molecule is said to have a structure that is a
resonance hybrid
Bonding in carbon compounds

• Benzene displaying resonance:

• Each unhybridized p orbital overlaps with two
other p orbitals, one on each of the two
neighbouring carbon atoms
• A large circular pi-type bond is formed above
and below the plane
• Electrons are delocalized in the benzene ring
Check point

• Name the concepts that can be used to

explain why carbon is able to form such
a wide range of organic compounds.
• Explain one of the concepts named
above.
Homologous series
• Organic compounds can be classified into well-defined groups called
homologous series
• The members of a homologous series conform to the following:
• They all have the same general formula
• Each member differs from its nearest neighbour by a molecular mass of 14 or a CH 2
group
• They all have the same functional group
• They have similar chemical properties due to the reactivity of the functional group
• Physical properties vary directly to the number of C atoms in the homologous series
Homologous series
All the members of a homologous series have
the same functional group
A functional group is an atom or a group of
atoms responsible for the chemical properties
of a compound
Do you remember?
• Can you draw and name:
• A straight alkane with 4 carbon atoms
• An alkane with 5 carbon atoms in the parent chain and
1 carbon atom branching from the 3rd carbon
• An alkene with 4 carbon atoms in a chain and the
double bond between the 2nd and 3rd carbon atoms
• A 3 carbon alcohol with the hydroxyl group on the 2
carbon atom in the chain
• An alkanoic acid with only 1 carbon atom
Types of formulae • 4. Condensed formula refers to the groups of atoms
arranged around each carbon atom in the compound. It
does not show the arrangement of the atoms. The
• Molecules can be illustrated in several ways, via condensed formula can be determined from the
empirical formula, molecular formula, structural or molecular formula e.g. butane is C4H10 and the
displayed formula, condensed formula or skeletal structural formula
formula
• 1. Empirical formula refers to the simplest whole Therefore the condensed formula is CH3CH2CH2CH3
number ratio of atoms in a compound. e.g. CH2
• 5. Skeletal formula refers to the bare structure of the
• 2. Molecular formula refers to the actual number of compound where carbon and single hydrogen atoms are
atoms in a compound e.g. C2H4 not shown. It is shown by a series of straight lines and
bends. An open end represents a –CH3 group which a
• 3. Structural / displayed formula refers to the
diagrammatic representation of an organic molecule “bend” represents a –CH2 group. If a double bond is
showing the arrangement of atoms e.g. present, the number of hydrogen atoms would decrease
appropriately. Other functional groups are shown
explicitly. E.g. butane is shown as and butan-
2-ol is represented by
Determining Empirical and Molecular Formulae
from experimental data
1. When a hydrocarbon was analyzed, it was 1. Combustion analysis of 1.0 g of a compound
containing only carbon, hydrogen and oxygen gives
found to contain 85.72% carbon and 14.28%
2.3 g of CO2 and 0.93 g of H2O. If the relative
hydrogen. If the molar mass of the
molecular mass of the compound is 58, determine the
compound was 56g/mol, determine its empirical and molecular formulae of the compound.
empirical and molecular formulae. 2. Ascorbic acid (vitamin C) contains carbon, hydrogen
2. Glucose is a sugar that is metabolised by the and oxygen. Combustion analysis of 0.528 g of
ascorbic acid gave 0.792 g of CO 2 and 0.216 g of H2O.
body to produce energy. Glucose is
composed of hydrogen, carbon and oxygen. (a) Determine the empirical formula of ascorbic acid.
The percentage composition is 40% C, 6.7% (b) If the molecular weight of ascorbic acid is 176
amu, what is the molecular formula?
H, and the remainder O. The molar mass is
180g/mol. Calculate the molecular formula.
Naming organic compounds
• When small organic compounds e.g. methane, ethane were discovered, they were assigned names that
seemed logical at the time
• As the number of known compounds rapidly increased over time, a more systematic naming system had
to be found
• The International Union of Pure and Applied Chemistry (IUPAC) assigned the responsibility for
designing an unambiguous nomenclature system to a committee that produced the IUPAC system of
nomenclature that is widely accepted today.
• They have developed several rules which are used to allocate names to the millions of organic
compounds that exist today

https://www.youtube.com/watch?v=U7wavimfNFE
Naming organic C1 to C10 straight-chain alkyl groups (branches)

compounds
We will look at this for the different
homologous series e.g.

C1 to C10 straight-chain alkanes

Naming organic
compounds
When compounds contain more than one
functional group, the order of precedence
determines which groups are named with prefix
– i.e. as substituents –, or suffix forms – i.e. as
part of the parent name of the molecule.
The highest precedence group takes the suffix,
with all others taking the prefix form.
NB. However, double and triple bonds only take
suffix form (-ene and -yne) and are used with
other suffixes.

https://www.masterorganicchemistry.com/2011/02/14/table-
of-functional-group-priorities-for-nomenclature/
 https://www.youtube.com/watch?v=HhT2E7wuAgg

Naming organic compounds - Alkanes

• Identify the longest unbranched chain of carbon • Assign a position, or locant, to the substituent
atoms in the molecule. Name the compound as a by numbering the parent chain starting from
derivative of this straight-chain alkane one end. We number the carbon atoms so that
• Identify the group or groups attached to the the position of the substituent is assigned the
longest or parent chain. Hydrogen atoms on the smallest number possible
parent hydrocarbon are regarded as having been
substituted by these groups, so the groups are
known as substituents.

• What is the longest continuous chain here?

• 6 carbons
• What prefix would be used for the parent chain?
• Hex (ane) • Hence, the name for this alkane is 3-methylhexane
• What is the name of the substituent?
• methyl
Naming organic compounds - Alkanes
• When the longest chain carries more than • If two substituents are attached to the same
one substituent, we number the chain in the carbon atom, the locant is shown for each
way that gives one of the substituents the substituent. Thus
• is 3-ethyl-3-methylhexane
smallest possible locant, and the numbers
assigned to the other substituents follow
• Name this compound:
• 4-ethyl-2-methylhexane • If the same alkyl substituent occurs twice,
the prefix ‘di-’ is used to form the name, and
the locant for each substituent is shown as
• NB. The name is written with the substituents placed in before
alphabetical order (not numerical order)

• 2,4-dimethylhexane 3,3-dimethylhexane
Check point

• Name the following compounds:

Draw the structure for each
compound:

4-ethyloctane
3-ethyl-2-methylpentane
3,3,5-trimethylheptane
cyclopentane
methylcyclobutane
Naming organic compounds - Alkenes
• Alkenes with four or more carbon atoms • What do you notice is different in the 2
can display structural isomerism structures of 2-butene?

• The position of the first unsaturated • How do we identify this difference when
naming?
carbon is given in the name to specify the
• Cis/trans isomers (We will look at this in detail
location of the double bond. So soon)
• CH3CH2CH=CH2 is 1-butene.
• If the molecule has more than one double
• Its isomer, CH3CH=CHCH3, is 2-butene.
bond, then the position of each must be
• There are however still 2 possible forms given, an ‘a’ is added to the prefix and di, tri
of 2-butene etc placed before the suffix, ‘ene’
Check point

• Name the following compounds:

Draw the structure for each
compound:

3-methyl-2-pentene
2-ethyl-1-hexene
cyclopentene
cyclohexene
 https://www.youtube.com/watch?v=VAmVdxEksxY

Naming organic compounds - Alcohols

• Like alkenes, the position of the hydroxyl • If more than one hydroxyl group is
group (-OH) must be given in the name present, the position of each must be
stated so that they have the lowest
possible locant number
• The prefix ends with “ane” and “di”, “tri” etc.
is place before the suffix, “ol”
Check point

• Name the following compounds:

Draw the structure for each
compound:

3-hexanol
3,3-dimethyl-2-butanol
Cyclobutanol
3,3-dibromo-2-methyl-2-
butanol
Naming organic compounds – Aldehydes &
Ketones
• For aldehydes, the ‘e’ in the name of the parent
• Compounds with the carbon-oxygen double bond alkane is changed to ‘al’
or carbonyl group (C=O) are called carbonyl • A locant is not needed since –CHO must be at the end of
compounds a chain

• These include the aldehydes and ketones

• Aldehydes have at least one H atom attached to
the carbonyl group
• Ketones have two R groups (aliphatic or aromatic)
attached to the carbonyl group • For ketones, the ending is changed to ‘one’
• The position of the C=O is shown by a locant at the start
of the name (except for the 1st two in the series); the
carbon skeleton is numbered to give the locant the
smallest possible number
Check point

• Name the following compounds:

Draw the structure for each
compound:

Butanal
2-methyl-propanedial
3,4-dihydoxy-2-butanone
1,2-cyclobutanedione
Naming organic compounds – Carboxylic acids
• The name of a carboxylic acid is
obtained by changing the -e of the
parent alkane to -oic acid
• The carbon chain includes the C of the –
COOH, which must be at the end of the
chain and is considered to be position 1
• The name does not need this locant to be
unambiguous, but the locants for
substituents on the chain must be shown
Check point

• Name the following compounds:

Draw the structure for each
compound:

2-methylpropanoic acid
ethanedioic acid
4-ethylpentanedioic acid (what’s
wrong with this name?)
Naming organic compounds – Aromatic
compounds
• Historically, benzene-like substances were called aromatic hydrocarbons because they had
distinctive aromas
• An aromatic compound is one which contains a benzene ring
• Naming aromatic compounds isn't quite so straightforward as naming chain compounds
• There are a few compounds that are almost always called by their common names
• These names are not always related to the name of the attached substituent group

https://www.chemguide.co.uk/basicorg/conventions/names3.html

https://chem.libretexts.org/Courses/Eastern_Mennonite_University/EMU%3A_Chemistry_for_t
he_Life_Sciences_(Cessna)/13%3A_Unsaturated_and_Aromatic_Hydrocarbons/13.8_Structure_
and_Nomenclature_of_Aromatic_Compounds
Naming organic compounds – Aromatic
compounds
Naming organic compounds – Aromatic
compounds
• Further rules are needed when the benzene ring has two substituents
attached.
• If the substituents are the same, the prefix di- is used.
• If the substituents are different, the names of the substituents are combined
and used as a prefix to ‘-benzene’, or the name of the substituent is used as a
prefix to the common name.
• The relative positions of the substituents are designated either by numbers or
by using the prefixes ortho (o), meta (m) or para (p). Note that ortho, meta
and para, or the letters o, m and p, are italicized in the compound names.
ortho means 1,2-, meta means 1,3- and para means 1,4-
Check point

• Name the following compounds:

Draw the structure for each
compound:

p-chloroiodobenzene
m-bromotoluene
4-chloroaniline
Isomerism

• There are two main types:- structural isomerism and stereoisomerism

• Structural isomerism occurs when 2 or more compounds have the same

molecular formulae but their atoms are arranged differently

• There are 3 categories of structural isomerism

• a) chain b) positional c) functional
Isomerism
• Chain isomers have same • Positional isomers show a • Functional isomers
molecular formula but difference in the position of have same molecular
differ in the length of the their functional group in formula but different
longest carbon atom chain the same chain. functional group.
• Example: • Example: • Example:
• Ethanol

• Dimethyl Ether
Isomerism

• Stereoisomerism occurs when 2 or more compounds have the same

molecular and structural formulae but the atoms are arranged differently in
space

• Stereoisomerism can be either a) geometric / cis-trans isomerism or b)

optical isomerism
Isomerism
• Geometric isomerism occurs in unsaturated • In (a) similar atoms either the Cl or the H are
compounds on OPPOSITE sides of THE DOUBLE BOND.
• With the presence of the multiple bond, rotation This configuration is called “trans”. While in
about the C=C bond is difficult without breaking (b) similar atoms are on the SAME side of
the bonds between them THE DOUBLE BOND, this configuration is
• Example called “cis”
• So
• compound (a) is trans-1,2-dichloroethene and
• Both (a) and (b) have the condensed formula
• compound (b) is cis-1,2-dichloroethene
CHClCHCl but the atoms are arranged differently
in space • Can you draw these 2 isomers of 2-butene?
Isomerism
• Optical isomerism occurs when there is • There is no line of symmetry one can
no symmetry about a carbon atom in a draw for this molecule
compound
• Therefore the molecule is
• For example Imagine a carbon atom with
four different atoms or groups of atoms asymmetric. Since there is no line of
attached to it symmetry about the central carbon
atom, that carbon atom is said to be
CHIRAL.
Isomerism
• Mirror images of compounds with chiral carbon • Enantiomers are identical in every way in terms of
atoms are said to be non-superimposable. Think of chemical and physical properties EXCEPT that one
trying to fit your left hand directly on top of your rotates plane polarised light to the left and the other
right hand. You would realise that they don’t fit rotates plane polarised light to the right by the same
neatly on each other. degree.
• Mirror images of compounds with chiral carbon • The enantiomer that rotates the plane to the right
(clockwise) is called dextrorotatory,
atoms are called enantiomers. The dotted line
• the enantiomer that rotates the plane to the left
represents the mirror line.
(counterclockwise) is called laevorotatory
• If there are equal concentrations of both enantiomers
in a mixture, there would be no observed optical
activity and the mixture would called a racemic
mixture or a racematate.
• Note: When showing chiral carbon atoms they MUST be indicated with
an asterisk next to it. (*)
Isomerism
• Many of the molecular building blocks, • For a similar reason, only one enantiomer
such as the amino acids that are used to of some medicinal compounds has a
make proteins, molecules essential for beneficial effect; the other enantiomer is
life, are chiral inactive or, in some cases, detrimental
• There is an absolute requirement that
only one enantiomer can be used • most famous of these is
thalidomide, which when
used to control morning
sickness in pregnant
women, resulted in the
birth of deformed children
Terminology
• Electrophile:- an electron loving species attracted • Inductive Effect:-
to negatively charged centres e.g. H+, Cl+, Br+, I-, • Some atoms or groups of atoms are electron
NO2+ withdrawing (pull electrons towards themselves) and
others are electron donating (push electrons away from
themselves).
• Nucleophile:- a nucleus loving species i.e. • Atoms or groups of atoms with electronegative atoms are
attracted to positively charged centres e.g. OH-, electron withdrawing and thus have a negative inductive
H2O, NH3, CN-, halide ion effect (-I),
• Atoms or groups of atoms like alkyl groups are electron
donating and have a positive inductive effect (+I)
• Hydrolysis:– the splitting of a molecule using • Mesomeric effect is the same as the inductive effect but it
water or in some cases the reaction of a molecule occurs in multiple bonds, while inductive effect occurs in
with water as opposed to simple dissolution single bonds.
Terminology
• Bonds must be first broken before a chemical reaction can
take place. In organic chemistry, bonds can be broken in
• Heterolytic fission :- breakage of a
two ways. covalent bond with atoms of
• a) homolytic fission and b) heterolytic fission
different electronegativities with
• Homolytic fission :- breakage of a covalent bond with
the formation of a cation and an
atoms of similar or same electronegativity resulting in the anion. The more electronegative
formation of free radicals. Each atom retain one electron
from the covalent bond. atom retains both electrons from the
covalent bond.
• NB Free radicals are highly reactive species with an
unpaired electron
Practice
• 1. a) What is tetravalency?
• b) Describe hybridization in the carbon atom.
• 2. How many structural isomers have the molecular formula C4H10?
• 3. a) Draw the fully displayed formula corresponding to CH2ClCHClCH3
• b) On the fully displayed formula you drew above, indicate the chiral carbon atom
with an asterisk.
• c) Draw the two enantiomers resulting from the chiral carbon atom you indicated
above in part b)
Practice

• 4. Using this condensed molecular formulae CH2ClCH2CH3

• Which type of structural isomerism can it exhibit?
• 5 i). Which compounds would exhibit optical isomerism?
• a) CH4 b) C2H6 c) CH3CHClBr (d) CH3CH2Cl
• ii) Draw the optical isomers for the compound you have chosen in 5 i)
• 6. But-2-ene is said to show “stereoisomerism”. Draw the cis and trans
isomers of but-2-ene
Practice
Practice
• Draw the structures below and identify which of the compounds are chiral?
Draw both enantiomers of the chiral molecules in a manner that makes clear that
they are mirror images of each other. Use the flying wedge convention.
• (a) 1-bromobutane
• (b) 2-bromobutane
• (c) 1-bromo-1-chlorobutane
• (d) 1-bromo-2-chlorobutane
• (e) 2-bromo-2-chlorobutane
• Naming organic compounds practice