ORGANIC CHEMISTRY

Unit 5
ORGANIC CHEMISTRY
 The study of carbon-containing compounds.
 Organic compounds contain backbones
comprised of chains and/or rings of carbon
and hydrogen atoms.
 Commonly used formulas are empirical,
molecular, structural (bond-line, condensed
and 3-D), which are most commonly used
over empirical, molecular formulas.
 HYDROCARBONS

• Compounds composed of only carbon and hydrogen atoms (C,

H).

• Acyclic (without rings); Cyclic (with rings); Saturated: only

carbon-carbon single bonds; Unsaturated: contains one or more
carbon-carbon double and/or triple bonds

• They represent a “backbone” when other “heteroatoms” (O, N,

S, .....) are substituted for H. (The heteroatoms give function to
the molecule.)

• Consider the bonding arrangements for (C, H, O, and N).

Particularly that each carbon has 4 bonds.
 SPECIAL NATURE OF CARBON - CATENATION
CATENATION is the ability to form bonds between atoms of the same element.
Carbon forms chains and rings, with single, double and triple covalent bonds, because it
is able to FORM STRONG COVALENT BONDS WITH OTHER CARBON ATOMS

Carbon forms a vast number of carbon compounds because of the strength of the C-C
covalent bond. Other Group IV elements can do it but their chemistry is limited due to the
weaker bond strength.

BOND ATOMIC RADIUS BOND ENTHALPY

C-C 0.077 nm +348 kJmol-1

Si-Si 0.117 nm +176 kJmol-1

The larger the atoms, the weaker the bond. Shielding due to filled inner orbitals and greater
distance from the nucleus means that the shared electron pair is held less strongly.
CONTENTS
Orbitals / Bonding / Shape
Atomic s and p orbitals
Orbitals / Bonding / Shape
Mixing Atomic Orbitals
Hybridization of s and p orbitals
 The atomic orbitals used in bond formation
determine the bond angles

• Tetrahedral bond angle: 109.5°

• Electron pairs spread themselves into space as far from
each other as possible
sp2 hybridization
A Triple Bond
sp-hybridization

• A triple bond consists of one  bond and two  bonds

with a bond order of 3.
•Triple bonds are shorter and stronger than double bonds
• There is a bond angle of the sp carbon: 180°
 HYDROCARBONS
• Alkanes contain only single ( ) bonds and have the
generic molecular formula: [CnH2n+2]

• Alkenes also contain double ( + ) bonds and have the

generic molecular formula: [CnH2n]

• Alkynes contain triple ( + 2) bonds and have the generic

molecular formula: [CnH2n-2]

• Aromatics are planar, ring structures with alternating

single and double bonds: eg. C6H6
 THE SPECIAL NATURE OF CARBON

CHAINS AND RINGS

CARBON ATOMS CAN BE ARRANGED IN

STRAIGHT CHAINS

BRANCHED CHAINS

and RINGS

You can also get a combination of rings and chains

CONTENTS
 Types of Hydrocarbons

Each C atom is tetrahedral with sp3 hybridized orbitals.

Each C atom is trigonal planar with sp2 hybridized orbitals.

There is no rotation about the C=C bond in alkenes.
 Types of Hydrocarbons

Each C atom is linear with sp hybridized orbitals.

Each C--C bond is the same length; shorter than a C-C bond: longer than a C=C bond.
The concept of resonance is used to explain this phenomena.
 QUESTION
An acyclic (noncyclic) hydrocarbon alkane has 12 carbon atoms.
How many hydrogen atoms would one molecule of the
compound possess?

A.12
B.24
C. 26
D. It would depend on more than just the number of carbon
atoms; it cannot be predicted without more information.
 THE SPECIAL NATURE OF CARBON

MULTIPLE BONDING AND SUBSTITUENTS

CARBON-CARBON COVALENT BONDS CAN BE SINGLE, DOUBLE OR TRIPLE

DIFFERENT ATOMS / GROUPS OF ATOMS CAN BE PLACED ON THE CARBONS

The basic atom is HYDROGEN but groups containing OXYGEN, NITROGEN,

HALOGENS and SULPHUR are very common.

CARBON SKELETON FUNCTIONAL CARBON SKELETON FUNCTIONAL

GROUP GROUP

The chemistry of an organic compound is determined by its FUNCTIONAL GROUP

CONTENTS
 THE SPECIAL NATURE OF CARBON

MULTIPLE BONDING AND SUBSTITUENTS

ATOMS/GROUPS CAN BE PLACED IN DIFFERENT POSITIONS ON A CARBON SKELETON

THE C=C DOUBLE BOND IS IN A DIFFERENT POSITION

PENT-1-ENE PENT-2-ENE

THE CHLORINE ATOM IS IN A DIFFERENT POSITION

1-CHLOROBUTANE 2-CHLOROBUTANE

CONTENTS
 TYPES OF FORMULAE - 1

MOLECULAR FORMULA C4H10

THE EXAMPLE BEING
The exact number of atoms of each
element present in the molecule USED IS... BUTANE

EMPIRICAL FORMULA C2H5

The simplest whole number ratio
of atoms in the molecule

CONDENSED STRUCTURAL FORMUL CH3CH2CH2CH3 CH3CH(CH3)CH3

The minimal detail using conventional
groups, for an unambiguous structure there are two possible structures

SKELETAL FORMULA H H H H H H H
Shows both the relative placing of atoms H C C C C H H C C C H
and the number of bonds between them H H H H H H
H C H
H
CONTENTS
Nomenclature: Alkanes
Names to Structures

1. For alkanes: C1,2,3,4- methane, ethane, propane,

butane; beyond C4, butane, add -ane to the Greek
root for the number of carbons.
C-C-C-C-C-C = hexane

2. Alkyl substituents: drop the -ane and add -yl.

-yl
-CH3 : methyl
-C2H5 : ethyl
 QUESTION
2,3-dimethylbutane has how many carbon atoms in its longest
continuous carbon chain?

A. 2
B. 3
C. 4
D. 6
Different Kinds of sp3 Carbon and
Associated Hydrogen Atoms
Unsaturated Hydrocarbons
Alkenes

 Alkenes contain C, H atoms and single and double bonds.

 The simplest alkenes are H2C=CH2 (ethene) and
CH3CH=CH2 (propene):
• Their trivial names are ethylene and propylene.
 Alkenes are named in the same way as alkanes with the
suffix -ene replacing the -ane in alkanes.
 The location of the double bond is indicated by a number.
 Geometrical (cis-trans) isomers are possible since there is
no rotation about a C=C  bond.
Unsaturated Hydrocarbons
Alkenes
Unsaturated Hydrocarbons
Alkenes
 QUESTION
How many hydrogen atoms would be part of
one molecule of cyclopentene?

A. 4
B. 5
C. 8
D. 10
Unsaturated Hydrocarbons
Alkynes

 Alkynes are hydrocarbons with one or more CC bond.

The triple bond in alkynes have one  and two  bonds
between two C atoms.
 Ethyne (acetylene) is a reactive alkyne: HCCH.
 When acetylene is burned in the presence of oxygen
(oxyacetylene torch) the temperature is about 3200 K.
 Alkynes are named in the same way as alkenes with the
suffix -yne replacing the -ene for alkenes.
Structures Names

Draw a bond-line structure for:

4-methyl-1-pentyne
Unsaturated Hydrocarbons
Aromatics

• Aromatic structures are formally related to benzene.

• Resonance forms provide for delocalized  electrons leading to equal
bond lengths. The net result is represented as a circle in the ring.
Substituted Benzenes:
Naming
Unsaturated Hydrocarbons
Aromatics
Functional Groups
“Functionality” relates to a chemically distinct, generally
reactive portion of a molecule.
 Alkanes do not have functionality.
 The simplest functional groups contain  electrons.
 Common functional groups contain heteroatoms,
elements other than C or H, in particular bonding
arrangements. Recognition of these patterns are essential to
understanding organic chemistry.
 NOTE: A generic representation, R-, can be used to
represent the entire C-H portion (backbone) of the
molecule.
 FUNCTIONAL GROUPS

Organic chemistry is a vast subject so it is easier to split it into small sections for study.
This is done by studying compounds which behave in a similar way because they have
a particular atom, or group of atoms, FUNCTIONAL GROUP, in their structure.

Functional groups can consist of one atom, a group of atoms or multiple bonds between
carbon atoms.

Each functional group has its own distinctive properties which means that the
properties of a compound are governed by the functional group(s) in it.

H H H H H H H H H H
H C C C C C NH2 H C C C C C OH
H H H H H H H H H H
Carbon Functional Carbon Functional
skeleton Group = AMINE skeleton Group = ALCOHOL

CONTENTS
Functional Groups:
Alcohols (R-OH)
 Alcohols contain -OH groups.
 The names are derived from the hydrocarbon name with
--ol in place of the -ane suffix. Example: ethane becomes
ethanol.
 Since the -O-H bond is polar, similar to H-O-H, alcohols
are quite soluble in water.
 CH3OH, methanol, is used as a gasoline additive and a
fuel. CH3CH2OH, ethanol is a legal recreational drug that
can be dangerous.
QUESTION
Functional Groups:
Alcohols (R-OH)

An important biological alcohol is cholesterol.

Cells cannot survive without it!
Functional Groups:
Ethers (R-O-R)
 Like alcohols ethers have an oxygen atom with
two single bonds.
 But instead of a hydrogen atom being bonded to
the oxygen as in alcohols, ethers have oxygen
bonded to two carbons (R-).
 Ethers are commonly used as solvents.
 Certain ethers are biologically active. Some are
used as anesthetics.
Compounds with a Carbonyl Group:
Aldehydes & Ketones
 The carbonyl functional group is C=O. Oxygen has a double bond.

 Aldehydes must have at least one H atom attached to the carbonyl

group:

 Ketones must have two C atoms attached to the carbonyl group:

Compounds with a Carbonyl Group:
Carboxylic Acids

 Carboxylic acids contain a carbonyl group with an -OH

attached.
 The “carboxylate” functional group is -COO-:

 Carboxylic acids are weak acids.

 Carboxylic acids are found in spinach, vinegar, cleaners,
vitamin C, aspirin, and citrus fruits.
 Carboxylic acids are also used to produce polymers used
in fibers, paints, and films.
Compounds with a Carbonyl Group:
Carboxylic Acids
QUESTION
Compounds with a Carbonyl Group:
Carboxylic Acid - Esters

 Most esters tend to have sweet, fruit like odors and are
used as food flavorings and scents.
 CH3COOCH2CH3
 Esters are named first using the alcohol part and then the
acid part; in the above example: ethyl from ethanol and
acetate from acetic acid.
 In the presence of a strong base, esters hydrolyze, the
ester molecule splits into an acid and an alcohol.
(saponification: the process used to make soap).
 QUESTION
Esters are often associated with the aromas and tastes of
fruits. The ester methyl butyrate is associated with
apples. What compounds would be observed if this
ester were to break down into its original components?

A.Methanal and butanone

B.Methanol and butanone
C.Methanol and butanoic acid
D.Methanoic acid and butanol
 Fats:
Esters of glycerol, a molecule with three -OH groups

Saturated vs. Unsaturated

Saponification, hydrolysis of an ester in the presence of a

base, is the reverse of esterification. Fats saponify to give
fatty acids plus glycerols. (eg.triglycerides)
Compounds with a Nitrogen atom:
Amines & Amides
 Amines are organic bases. They are weak bases.
 Just as alcohols can be thought of organic forms of water, amines
can be thought of organic forms of ammonia:

 Amides are composites of carbonyl and amine functionalities:

-
 QUESTION
The compound diethyl amine that can be used as a
curing agent in some epoxy materials would have
how many hydrogen atoms per molecule?

A.7
B.10
C.11
D.12
 COMMON FUNCTIONAL GROUPS

GROUP ENDING GENERAL FORMULA EXAMPLE

ALKANE - ane RH C2H6 ethane

ALKENE - ene C2H4 ethene

ALKYNE - yne C2H2 ethyne

HALOALKANE halo - RX C2H5Cl chloroethane

ALCOHOL - ol ROH C2H5OH ethanol

ALDEHYDE -al RCHO CH3CHO ethanal

KETONE - one RCOR CH3COCH3 propanone

CARBOXYLIC ACID - oic acid RCOOH CH3COOH ethanoic acid

ACYL CHLORIDE - oyl chloride RCOCl CH3COCl ethanoyl chloride

AMIDE - amide RCONH2 CH3CONH2 ethanamide

ESTER - yl - oate RCOOR CH3COOCH3 methyl ethanoate

NITRILE - nitrile RCN CH3CN ethanenitrile

AMINE - amine RNH2 CH3NH2 methylamine

NITRO nitro- RNO2 CH3NO2 nitromethane

SULPHONIC ACID - sulphonic acid RSO3H C6H5SO3H benzene sulphonic acid

ETHER - oxy - ane ROR

CONTENTS C2H5OC2H5 ethoxyethane
 Bond-line structures (omitting H atoms).

ketone
1.
aldehyde
2.
carboxylic acid
3.
ester (carboxylic acid ester)
4.
 COMMON FUNCTIONAL GROUPS

ALKANE CARBOXYLIC ACID

ALKENE

ALKYNE
ESTER
HALOALKANE

ACYL CHLORIDE
AMINE

NITRILE
AMIDE
ALCOHOL

ETHER
NITRO

ALDEHYDE

SULPHONIC ACID
KETONE

CONTENTS
QUESTION
Identify the functional groups in the following
molecule.

A) Alcohol, amide, carboxylic acid

B) Aldehyde, amine, ester

C) Alcohol, amine, carboxylic acid
D) Aldehyde, amide, ketone
 HOW MANY STRUCTURES?

Draw legitimate structures for each molecular formula and classify each one according
to the functional group present. Not all the structures represent stable compounds.

carbon atoms have 4 covalent bonds surrounding them

oxygen atoms 2
nitrogen atoms 3
hydrogen 1
halogen atoms 1

C2H6 ONE

C3H9Br TWO

C4H8 FIVE - 3 with C=C and 2 ring compounds with all C-C’s

C2H6O TWO - 1 with C-O-C and 1 with C-O-H

C3H6O SIX - 2 with C=O, 2 with C=C and 2 with rings

C2H7N TWO

C2H4O2 SEVERAL - Only 2 are stable

C2H3N TWO CONTENTS

 HOW MANY STRUCTURES?

Draw legitimate structures for each molecular formula and classify each one according
to the functional group present. Not all the structures represent stable compounds.

carbon atoms have 4 covalent bonds surrounding them

oxygen atoms 2
nitrogen atoms 3
hydrogen 1
halogen atoms 1

C2H6 ONE

C3H9Br TWO

C4H8 FIVE - 3 with C=C and 2 ring compounds with all C-C’s

C2H6O TWO - 1 with C-O-C and 1 with C-O-H

C3H6O SIX - 2 with C=O, 2 with C=C and 2 with rings

C2H7N TWO

C2H4O2 SEVERAL - Only 2 are stable

C2H3N TWO CONTENTS

 NOMENCLATURE

Ideally a naming system should tell you everything about a structure without ambiguity.
There are two types of naming system commonly found in organic chemistry;

Trivial : based on some property or historical aspect;

the name tells you little about the structure
Systematic : based on an agreed set of rules (I.U.P.A.C);
exact structure can be found from the name (and vice-versa).

HOMOLOGOUS SERIES
trivial name systematic name example(s)
paraffin alkane methane, butane
olefin alkene ethene, butene
fatty acid alkanoic (carboxylic) acid ethanoic acid

INDIVIDUAL COMPOUNDS
trivial name derivation systematic name
methane methu = wine (Gk.) methane (CH4)
butane butyrum = butter (Lat.) butane (C4H10)
acetic acid acetum = vinegar (Lat.) ethanoic acid (CH3COOH)

CONTENTS
 I.U.P.A.C. NOMENCLATURE
A systematic name has two main parts.

STEM number of carbon atoms in longest chain bearing the functional group +
a prefix showing the position and identity of any side-chain substituents.

Apart from the first four, which have trivial names, Prefix C atoms Alkane
the number of carbons atoms is indicated by a meth- 1 methane
prefix derived from the Greek numbering system. eth- 2 ethane
prop- 3 propane
but- 4 butane
The list of alkanes demonstrate the use of prefixes. pent- 5 pentane
hex- 6 hexane
The ending -ane is the same as they are all hept- 7 heptane
alkanes. oct- 8 octane
non- 9 nonane
dec- 10 decane

Working out which is the longest chain can pose a problem with larger molecules.

CONTENTS
 I.U.P.A.C. NOMENCLATURE
How long is a chain?

Because organic molecules are three dimensional and paper is two dimensional it
can confusing when comparing molecules. This is because...

1. It is too complicated to draw molecules with the correct bond angles

2. Single covalent bonds are free to rotate

All the following written structures are of the same molecule - PENTANE C5H12

CH3
CH3 CH2 CH2 CH2 CH3
CH2 CH2 CH2 CH3
CH3
CH2 CH2 CH2 CH3 CH2 CH3
CH3 CH2 CH2

A simple way to check is to run a finger along the chain and see how many carbon
atoms can be covered without reversing direction or taking the finger off the page.
In all the above there are... FIVE CARBON ATOMS IN A LINE.
CONTENTS
 I.U.P.A.C. NOMENCLATURE
How long is the longest chain?

Look at the structures and work out how many carbon atoms are in the longest chain.

CH3
THE ANSWERS ARE
CH2 ON THE NEXT SLIDE

CH3 CH CH2 CH3

CH3
CH3 CH2 CH2 CH2 CH CH3

CH3
CH3 CH2
CH3 CH2 CH CH CH3

CONTENTS
 I.U.P.A.C. NOMENCLATURE
How long is the longest chain?

Look at the structures and work out how many carbon atoms are in the longest chain.

CH3
CH2 LONGEST CHAIN = 5

CH3 CH CH2 CH3

CH3 LONGEST CHAIN = 6

CH3 CH2 CH2 CH2 CH CH3

CH3
CH3 CH2 LONGEST CHAIN = 6
CH3 CH2 CH CH CH3

CONTENTS
 I.U.P.A.C. NOMENCLATURE
A systematic name has two main parts.

SUFFIX An ending that tells you which functional group is present

See if any functional groups are present.

Add relevant ending to the basic stem. Functional group Suffix
ALKANE - ANE
ALKENE - ENE
In many cases the position of the functional
ALKYNE - YNE
group must be given to avoid any ambiguity
ALCOHOL - OL
ALDEHYDE - AL
KETONE - ONE
ACID - OIC ACID

1-CHLOROBUTANE 2-CHLOROBUTANE

SUBSTITUENTS Many compounds have substituents (additional atoms, or groups)

attached to the chain. Their position is numbered.

CONTENTS
 I.U.P.A.C. NOMENCLATURE
SIDE-CHAIN carbon based substituents are named before the chain name.
they have the prefix -yl added to the basic stem (e.g. CH3 is methyl).

Alkyl radicals methyl CH3 - CH3

ethyl CH3- CH2- C2H5
propyl CH3- CH2- CH2- C3H7

Number the principal chain from one end to give the lowest numbers.
Side-chain names appear in alphabetical order butyl, ethyl, methyl, propyl
Each side-chain is given its own number.
If identical side-chains appear more than once, prefix with di, tri, tetra, penta, hexa
Numbers are separated from names by a HYPHEN e.g. 2-methylheptane
Numbers are separated from numbers by a COMMA e.g. 2,3-dimethylbutane

CONTENTS
 I.U.P.A.C. NOMENCLATURE
SIDE-CHAIN carbon based substituents are named before the chain name.
they have the prefix -yl added to the basic stem (e.g. CH3 is methyl).

Alkyl radicals methyl CH3 - CH3

ethyl CH3- CH2- C2H5
propyl CH3- CH2- CH2- C3H7

Number the principal chain from one end to give the lowest numbers.
Side-chain names appear in alphabetical order butyl, ethyl, methyl, propyl
Each side-chain is given its own number.
If identical side-chains appear more than once, prefix with di, tri, tetra, penta, hexa
Numbers are separated from names by a HYPHEN e.g. 2-methylheptane
Numbers are separated from numbers by a COMMA e.g. 2,3-dimethylbutane

Example longest chain 8 (it is an octane)

CH3 CH3
3,4,6 are the numbers NOT 3,5,6
order is ethyl, methyl, propyl CH3 CH2 CH2 CH CH2
3-ethyl-5-methyl-4-propyloctane CH3 CH2 CH2 CH CH CH2 CH3
CONTENTS
 I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes
THE ANSWERS ARE ON THE NEXT SLIDE

CH3
CH2
CH3 CH CH2 CH3

CH3
CH3 CH2 CH2 CH2 CH CH3

CH3
CH3 CH2
CH3 CH2 CH CH CH3

CONTENTS
 I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes

CH3
CH2
CH3 CH CH2 CH3

CH3
CH3 CH2 CH2 CH2 CH CH3

CH3
CH3 CH2
CH3 CH2 CH CH CH3

CONTENTS
 I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes

Longest chain = 5 so it is a pentane

CH3
A CH3, methyl, group is attached to the
CH2 third carbon from one end...
CH3 CH CH2 CH3 3-methylpentane

CH3
CH3 CH2 CH2 CH2 CH CH3

CH3
CH3 CH2
CH3 CH2 CH CH CH3

CONTENTS
 I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes

Longest chain = 5 so it is a pentane

CH3
A CH3, methyl, group is attached to the
CH2 third carbon from one end...
CH3 CH CH2 CH3 3-methylpentane

Longest chain = 6 so it is a hexane

CH3
A CH3, methyl, group is attached to the
CH3 CH2 CH2 CH2 CH CH3 second carbon from one end...
2-methylhexane

CH3
CH3 CH2
CH3 CH2 CH CH CH3

CONTENTS
 I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes

Longest chain = 5 so it is a pentane

CH3
A CH3, methyl, group is attached to the
CH2 third carbon from one end...
CH3 CH CH2 CH3 3-methylpentane

Longest chain = 6 so it is a hexane

CH3
A CH3, methyl, group is attached to the
CH3 CH2 CH2 CH2 CH CH3 second carbon from one end...
2-methylhexane

Longest chain = 6 so it is a hexane

CH3
CH3, methyl, groups are attached to the
CH3 CH2 third and fourth carbon atoms
(whichever end you count from).
CH3 CH2 CH CH CH3
3,4-dimethylhexane
CONTENTS
 NAMING ALKENES

Length In alkenes the principal chain is not always the longest chain
It must contain the double bond
the name ends in -ENE

Position Count from one end as with alkanes.

Indicated by the lower numbered carbon atom on one end of the C=C bond

5 4 3 2 1
CH3CH2CH=CHCH3 is pent-2-ene (NOT pent-3-ene)

Side-chain Similar to alkanes

position is based on the number allocated to the double bond

1 2 3 4 1 2 3 4
CH2 = CH(CH3)CH2CH3 CH2 = CHCH(CH3)CH3
2-methylbut-1-ene 3-methylbut-1-ene

CONTENTS
 Isomerism
• Molecules which have the same molecular
formula, but differ in the arrangement of
their atoms, are called isomers.
• Constitutional (or structural) isomers differ
in their bonding sequence.
• Stereoisomers differ only in the
arrangement of the atoms in space.
 Geometric Isomerism
Br Br Br CH3
C C and C C
H3C CH3 H3C Br

cis – or (Z-) same side trans – or (E-) across

cis-trans isomers are geometric isomers.

There must be two different groups on the sp2 carbons.
 Geometric Isomerism

No cis-trans isomers in top two isomers, only the bottom two.