ORGANIC CHEMISTRY

Organic chemistry is the study of carbon containing

compounds
There are over 7 million organic compounds known and
90% of all new compounds synthesized are organic

Classification of organic compounds

 Hydrocarbons are made up of only carbon and
hydrogen
Saturated hydrocarbons have only single bonds
Unsaturated hydrocarbons have multiple bonds
Hydrocarbons are classified into the following groups:

 Hydrocarbon derivatives have atoms of other elements

such as oxygen, nitrogen, halogens, sulfur, etc.
Hydrocarbon derivatives have specific arrangements of
atoms called ‘functional groups’
The following diagram shows some of the classes of
hydrocarbon derivatives based on their structures:

1
Functional Groups
A functional group is a small group of atoms that is
responsible for the chemical behavior of the molecule
Functional groups consisting of carbon atoms only:
Functional Class Example IUPAC
Group (Family) Name Name
Alkene H2C=CH2 Ethene
CC Alkyne HCCH Ethyne
Arene C6H6 Benzene

2
Functional groups with single bonded atoms:
Functional Class Example IUPAC
Group (family) Name Name
X Iodo
Alkyl Halide H3C-I
(X=Br,I,Cl,F) methane
OH Alcohol CH3CH2OH Ethanol
Ethylmethyl
O Ether CH3OCH2CH3
ether
Amino
Amine H3C-NH2
methane
Functional Groups with multiple bonded atoms:
Functional Class (family) Example IUPAC
Group Name Name
O
Aldehyde H3CCHO Ethanal
C H
O
Ketone H3CCOCH3 Propanone
C
O Carboxylic Ethanoic
H3CCO2H
C O H Acid Acid
O Ethyl
Ester H3CCO2CH2CH3
C O ethanoate

3
Formulas of organic compounds
Organic compounds are represented by different formulas
For example, the structural formulas of straight chain
pentane (C5H12) consists of the following:
Extended formula Condensed formula
CH3CH2CH2CH2CH3

Line formula

Distinguishing (categorizing) carbon atoms

A primary carbon (1º) is one that is bonded to only one
other carbon atom
A secondary carbon (2º) is bonded to two other carbon
atoms
A tertiary (3º) and quaternary (4º) carbon atoms are
bonded respectively to three and four other carbons
The following diagram illustrates the different categories of
carbon:

4
Nomenclature of organic compounds
The IUPAC nomenclature system is a set of rules used by
organic chemists to name organic compounds

Hydrocarbon compounds
Alkanes (saturated hydrocarbon)
 Alkanes consist entirely of C-C and C-H single bonds
 General molecular formula: CnH2n+2 where n = number
of carbon atoms in the molecule
 They have only sp3 hybridized carbons, thus are
tetrahedrally shaped and non-polar (dissolves only in
organic solvents not in water)

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 Straight chain alkanes have all carbons attached in a
row, branched chain alkanes have branching
connections and cycloalkanes are arranged in rings
(Alkanes have no functional groups but constitute the
framework for other classes of compounds)

A homologous series is a series of compounds that

differ in succession by a constant increase in C and H
from one member to another
The following table shows a homologous series:
Molecular Structural IUPAC Name
Formula Formula
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

CH4 CH4 Methane

C2H6 CH3-CH3 Ethane
C3H8 CH3-CH2-CH3 Propane
C4H10 CH3-(CH2)2-CH3 Butane
C5H12 CH3-(CH2)3-CH3 Pentane
C6H14 CH3-(CH2)4-CH3 Hexane
C7H16 CH3-(CH2)5-CH3 Heptane
C8H18 CH3-(CH2)6-CH3 Octane
C9H20 CH3-(CH2)7-CH3 Nonane
C10H22 CH3-(CH2)8-CH3 Decane
*The base (root or parent) names are underlined

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The following table lists the IUPAC names assigned to
alkanes from C-1 to C-10:
Name Molecular Structural Isomers
Formula formula
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

methane CH4 CH4 1

ethane C2H6 CH3CH3 1
propane C3H8 CH3CH2CH3 1
butane C4H10 CH3CH2CH2CH3 2
pentane C5H12 CH3(CH2)3CH3 3
hexane C6H14 CH3(CH2)4CH3 5
heptane C7H16 CH3(CH2)5CH3 9
octane C8H18 CH3(CH2)6CH3 18
nonane C9H20 CH3(CH2)7CH3 35
decane C10H22 CH3(CH2)8CH3 75

The IUPAC names for some substituent groups

(branches) that may be attached to the unbranched
chains are given in the following table
Note: Substituents consisting of C-H only are known as
alkyl groups
The symbol R, R’ or R” is used to designate
unspecified alkyl groups
The ‘ane’ suffix in alkanes is replaced by ‘yl’

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Substituents Name Substituents Name
CH3- Methyl CH3(CH2)2CH2- Butyl
C2H5- Ethyl (CH3)2CHCH2- Isobutyl
CH3CH2CH2- Propyl CH3CH2CH(CH3)- sec-Butyl
(CH3)2CH- Isopropyl (CH3)3C- tert-Butyl
Br Bromo Cl Chloro
F Fluoro I Iodo
NO2 Nitro OH Hydroxy
Benzyl Phenyl

Alkenes and Alkynes (unsaturated hydrocarbons)

 Alkenes consist of at least one C=C bonds [one 
(strong) + one  (weak) bond]
- General molecular formula: CnH2n where n = number
of carbon atoms in the molecule
- Each double bond reduces the number of hydrogen
atoms by 2
- The double bonds cannot rotate and remain fixed in
space
- The Pi bond breaks during a reaction without
disturbing the sigma bond
- Alkenes have only sp2 hybridized carbons that are
trigonal planar shaped

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 Alkynes have at least one CC bonds [one  and two 
bonds]
- General molecular formula: CnH2n-2 where n = number
of carbon atoms in the molecule
- Each triple bond reduces the number of hydrogen
atoms by 4
- The triple bonds cannot rotate and remain fixed in
space
- The two Pi bond breaks during a reaction without
disturbing the sigma bond
- The geometry around the two sp carbons is ‘linear’
Aromatic hydrocarbons
- Aromatic hydrocarbons are cyclic hydrocarbons with
benzene rings
- The generic notation for an aryl group is Ar
- The two commonly encountered substituent groups are
‘phenyl’ and ‘benzyl’, for example

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- They are water insoluble and carcinogenic (cancer
causing) if exposed with sufficient concentration/time
- Most have a sweet aroma hence the reason for the
name ‘aromatic’
Alcohols
- Alcohols consist of the hydroxyl group (OH) and are
represented by the general formula (ROH)
- Monohydric alcohols have only one hydroxyl group in
them
- Polyhydric alcohols have two or more hydroxyl groups
in them
The (OH) group can be categorized into 3 types:
A primary alcohol (1º) has the (OH)
group bonded to a primary carbon

A secondary alcohol (2º) has the (OH)

group bonded to a secondary carbon

A tertiary (3º) alcohol has the (OH)

group bonded to the tertiary carbon

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Aldehydes and Ketones
- Aldehydes and ketones are
compounds that have a carbonyl
or acyl group
- They are also known as carbonyl compounds
- Aldehydes have the H atom
attached to the acyl group: the
general formula is
- Ketones have another alkyl
group attached to the acyl group:
the generic formula is
- Aldehydes and ketones have similar chemical activity
Carboxylic acids and Esters
- Carboxylic acids consist of the carboxyl group (COOH
or CO2H)
- The general formula for carboxylic
acids is
- They are also known as organic
acids
- Esters are derivatives of
carboxylic acids with the general
formula

11
Ethers
- The functional group in ethers is
called the alkoxy group
- The general formula for ethers is
- Symmetrical ethers have the same alkyl groups
- Assymetrical ethers have different R and R’ groups

ORGANIC NOMENCLATURE
Organic compounds are divided into several different
families or groups (the name will vary slightly depending
on which group it is in)
In general, each name has the following components:
Prefix - Parent (root) Name - Suffix
 The prefix identifies each of the substituents and gives
the location of the substituents and functional group
 The parent name is the number of Carbon atoms in the
longest continuous chain
 The suffix indicates the family group (it identifies the
functional group(s) present in the molecule)
General rules for naming organic compounds:
1) Determine the Parent name
 Count each continuous chain to find the longest
(some chains may turn corners)
 Name the Parent, according to the number of C
atoms in the longest continuous chain (refer to the
list of Parent names)
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  If you have two chains which are equal in length,
choose the one with the larger number of branches
 If the parent chain is cyclical, add the word ‘cyclo’
preceding (before) the Parent name
 When naming a molecule other than an alkane, the
parent chain must include the functional group(s)

2) Assign each carbon atom in the parent chain a

number
 Begin counting the parent chain at the end nearer

the first branch

 If the first branch occurs at the same carbon number

when counting from either end of the parent chain,

then begin at the end that gives the lowest number
for the second branch
 When naming a molecule other than an alkane,

number the chain so that the lowest number is given

to the first carbon of the functional group
3) Name the prefix
 Identify each substituent present. Once identified,

the substituent name can be assigned (refer to the

list of substituent names)
 Count the number of each identical substituents.

Give the substituent name a prefix according to the

number of identical substitutents present (refer to
the list of prefixes)
 Assign a number to each substituent, matching the

number of the carbon atom where it attaches to the

parent chain. Preceding the name of each
substituent and prefix to substituent, give the
number for the substituent followed by a hyphen (-)
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  If two substituents are present on the same carbon
atom, assign them both the same number.
 Write the Prefix as a single word, using hyphens

(-) to separate the different substituent names and

commas (,) to separate the numbers
 List the substituent names alphabetically, according

to the root name

4) Name the Suffix
 The suffix name is determined by the family name

(refer to the list of functional groups)

 If more than one different functional groups are

present, list their suffixes in alphabetical order, with

hyphenated numbers used to indicate the carbon
number of the parent chain that they are bonded to
 If more than one identical functional group is

present, give the suffix a prefix according to the

number present (refer to the list of prefixes)
List of Parent names (or root names)
# of C's Parent name # of C's Parent name
1 meth 11 undec
2 eth 12 dodec
3 prop 13 tridec
4 but 14 tetradec
5 pent 15 icos
6 hex 16 henicos
7 hept 17 docos
8 oct 18 triacont
9 non 19 tetracont
10 dec 20 pentacont

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List of substituent names
Substituent Formula Name of Substituent
R-Cl Chloro
R-Br Bromo
R-I Iodo
R-F Fluoro
R-CH3 Methyl
R-CH2CH3 Ethyl
R-CH2CH2CH3 Propyl
CH3CHRCH3 Isopropyl
R-CH2CH2CH2CH3 Butyl
CH3CHRCH2CH3 sec-butyl
R-C(CH3)3 t-Butyl
R-CH2CH(CH3)2 Isobutyl
R-CH2CH2CH2CH2CH3 Pentyl
Key: t = tertiary, sec = secondary

List of prefixes
Name # of substituents Name # of substituents
mono 1 hepta 7
di 2 oxo 8
tri 3 nona 9
tetra 4 deca 10
penta 5 undeca 11
hexa 6 dodeca 12
*mono may be omitted from the name

List of functional groups (suffixes)

Functional Group Suffix name Functional Group Suffix name
alkane ane Alkene ene
alkyne yne Alcohol ol
Ether ether Amine amine
Nitrile nitrile Sulfide sulfide
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 Thiol thiol Aldehyde al
Ketone one Carboxylic Acid oic acid
Ester oate Amide amide

Naming aromatic hydrocarbons

Some mono-substituted aromatics compounds are
named by using the suffix ‘benzene’

A majority of these compounds, however, are referred to

by singular names that are unique

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When more than one substituent is present on a benzene
ring, the relative locations of the substituents are
designated by prefixes ‘Ortho’, ‘Meta’ and ‘Para’ that are
used to indicate a 1,2- or 1,3- or 1,4- relationship
respectively

Examples:
ortho-dimethylbenzene
or
1,2-dimethylbenzene

meta-dimethylbenzene
or
1,3-dimethylbenzene

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 Examples of compound names
Alkanes
C H3 CH CH 2 CH CH Assign numbers
2 4 3
7 6 5
3 CH CH Name prefix: 2,4-dimethyl
3
2 CH
2
Name suffix: hept + ane
1 CH Name:
3
2,4-dimethyl heptane
Determine longest chain

8 7 6 5 4 3 2 1 Name prefix: 5-ethyl-3,4-

CH CH CH2 CH CH CH CH2 CH
3 2 3 dimethyl
CH2 CH CH
3 3 Name suffix: oct + ane
CH
3 Name:
Determine longest chain 5-ethyl-3,4-dimethyl
Assign numbers octane

Cl Assign numbers
C H 3 CH CH Br Name prefix: 3-bromo-2-
1 2 3 chloro
4 CH 2 Name suffix: pent + ane
5 CH
3
Name:
Determine longest chain 3-bromo-2-chloropentane

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 Cycloalkanes
Cl Assign numbers on ring
1 Name prefix: 1-chloro-3-methyl-
5 2 Name suffix: cyclopent + ane
Name:
CH 3
4 3 1-chloro-3-methyl cyclopentane

Alkenes
CH CH CH CH CH CH3 Assign numbers
3 2 2
1 2 3 4 5 6 Name prefix: -
Determine longest chain Name suffix: 2-hex + ene
with functional group Name: 2-hexene
1 2 3 4 5 6 7 Name prefix: 4-ethyl-2,6-
CH CH CH C CH CH CH
3 2 3 dimethyl-
CH CH CH CH3 Name suffix: 3-hept + ene
3 2 3
Determine longest chain Name:
with functional group 4-ethyl-2,6-dimethyl-3-
Assign numbers heptene

CH CH CH CH CH CH3 Name prefix: -

3 2
6 5 4 3 2 1 Name suffix: 1,4-hex +
Determine longest chain diene
with functional group Name: 1,4-hexadiene
Assign numbers

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 1

2
Name prefix: 3-methyl
5
Name suffix: 1-cyclopent
CH 3
+ ene
4 3
Name:
C with functional group 3-methyl-1-cyclopentene
smallest number

Alkynes
6 5 4 3 2 1
CH CH CH C C CH 3 Assign numbers
3 2
CH3 Name prefix: 4-methyl-
Determine longest chain Name suffix: 2-hex+ yne
with functional group Name: 4-methyl-2-hexyne

7 6 5 4 3 2 1
CH CH CH CH C
3 2 2
C CH Cl
2 Name prefix: 1-chloro-4-
methyl-
CH
3 Name suffix: 2-hept+yne
Determine longest chain Name:
with functional group 1-chloro-4-methyl-2-
Assign numbers heptyne

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 Aromatic hydrocarbons
Br Assign numbers on benzene ring
1 Br Name prefix: 1,2-dibromo
2 Name suffix: benzene
Name: 1,2-dibromobenzene
Br Assign numbers on benzene ring
Br Name prefix: 1,2,4-tribromo-5-
methyl
Name suffix: benzene
CH 3 Name: 1,2,4-tribromo-5-methyl
Br benzene
Alcohols
Determine longest chain with
functional group
Assign numbers
Name prefix: 2-methyl-
Name suffix: 2-pentan + ol
Name: 2-methyl-2-pentanol
Assign numbers
Name prefix: -
Name suffix: 1,2-propan +
Determine longest chain diol
with functional group Name: 1,2-propandiol

21
 Aldehydes

Assign numbers
Name prefix: -
Name suffix: 1-propan + al
Determine longest chain Name: propanal
with functional group

Assign numbers
Name prefix: 2-methyl-3-
phenyl-
Name suffix: pentan + al
Determine longest chain Name: 2-methyl-3-phenyl
with functional group pentanal

Ketones

Assign numbers
Name prefix: -
Determine longest chain Name suffix: 2-propan+ one
with functional group Name: 2-propanone

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 Assign numbers
Name prefix: 3-methy-4-
phenyl-
Name suffix: 2-hexan + one
Determine longest chain Name: 3-methyl-4-phenyl
with functional group hexanone
Generic name (for < 5
carbons)
Ethyl methyl ketone

Carboxylic acids
Assign numbers
Name prefix: -
Name suffix: ethan + oic
Determine longest chain acid
with functional group Name: Ethanoic acid
Assign numbers
Name prefix: 2-methyl-3-
phenyl-
Name suffix: pentan + ioc
acid
Determine longest chain Name: 2-methyl-3-phenyl
with functional group pentanoic acid
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 Ester
Assign numbers
Name prefix: ethyl-
Name suffix: 2-methyl-3-
phenyl-butan + oate
Name: ethyl-2-methyl-3-
Determine longest chain phenyl butanoate
with functional group

Generic name (C < 5)

Ethyl methyl ester

Ether

Generic name (C < 5)

Determine longest chain Ethoxymethane
from functional group IUPAC name
Assign numbers Ethyl methyl ether

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Writing structures of organic compounds
Write the structural formula of the following compounds:
(a) 2,4-dimethyl-3-ethylpentane
Determine the parent chain C C C C C
1 2 3 4 5
and assign numbers
Add substituents: CH 3 CH 3
3
ethyl at C-3 and methyl at C C C C C
C-2 and 4 1 2 4 5
CH 2 CH 3

Complete the number of H's CH 3 CH 3

CH CH CH CH CH 3
3
CH 2 CH3

(b) Methylcyclopropane
Determine the parent chain C
and assign numbers and C C CH
3
add substituents
Complete the number of H's CH2

CH2 CH CH
3

25
(c) 3-isopropyl-hexene
Determine the parent C C C C C C
chain / assign numbers 1 2 3 4 5 6
Add substituents 3
C C C C C C
1 2 4 5 6
CH CH CH
3 2 3

Complete the number of

H atoms

(d) 6-methyl-2-ethyl phenol

Determine parent chain OH
1
and assign numbers 6 2

5 3
4

Add substituents OH
Complete the number of CH CH CH
3 2 3
H on the substituents

26
Isomerism in hydrocarbons
1) Structural isomers are compounds that have the same
molecular formula but different structures
eg Stuctural isomers of pentane (C5H12) are:

2) Geometric Isomers (or stereoisomers) are compounds

that have the same molecular formula but have
different spatial arrangement within the molecule
 The cis configuration have identical substituents on
the same side of the double bond
 The trans configuration have Identical groups on
apposite sides of the double bond
For example the geometric isomers for 2-butene
(CH3CH=CHCH3) are

27
3) Optical isomers are a pair of non superimposible
mirror image compounds
A molecule with optical isomers have an sp3 carbon
atom with different groups attached (called a chiral
carbon or chiral center)
For example the optical isomers for CH3CHClBr are:

Center for mirror symmetry is denoted by (*) and is

refered to as a “chiral carbon”

Visual (classification) tests for organic compunds

Test for unsaturated hydrocarbon (C=C and CC)
(1) Bromine test for alkene and alkyne
Procedure: Dilute bromine solution (in CH2Cl2) is
added to the sample and shaken
Positive test: Yellow color of bromine is discharged
(disappears) for alkenes and alkynes

28
Alkene

Alkyne

(2) Baeyer test (KMnO4)

Procedure: Aqueous solution of KMnO4 is added to
the sample and shaken
Positive test: The disappearance of the purple color of
KMnO4 and the appearance of a brown suspension of
MnO2 is a positive test

Alkene

Alkyne

29
Lucas Test for Secondary and Tertiary Alcohols
Procedure: The Lucas reagent is added to the sample at
room temperature, shaken vigorously and allowed to
stand. The time required for the formation of the alkyl
chloride (an insoluble layer or emulsion) is noted
Positive test: Appearance of a cloudy second layer or
emulsion
 3 alcohols: almost immediately
o

 2 alcohols: 5 -10 minutes

o

 1 alcohols: no reaction at all

o

Alcohol

Tests for Aldehydes and Ketones

(1) 2,4-DNP Test for aldehydes and ketones
Procedure: The 2,4-dinitrophenylhydrazine reagent (DNP
reagent) and ethanol is added to the sample and shaken
vigorously. If no precipitate forms immediately, allow the
solution to stand for 15 minutes
Positive test: The formation of a yellowish precipitate
shows the presence of aldehydes or ketones

30
Ketone
or
aldehyde

(2) Tollen’s test for aldehydes

Procedure: Freshly prepared Tollen’s reagent is added to
the sample (gentle heating can be employed if no reaction
is immediately observed)
Positive test: Formation of silver mirror or a black
precipitate is a positive test

Aldehyde

(3) Iodoform Test for methyl ketones

Procedure: A mixture of 3 M NaOH and iodine solution is
added to the sample solution and shaken vigorously

31
Positive test: Formation of solid iodoform (yellow
precipitate) is a positive test

Test for carboxylic acids

Sodium carbonate test

Procedure: Saturated NaHCO3 and methanol is added to

the sample
Positive test: Production CO2 is a positive test for the
presence of the carboxylic acid
Test for halides
Procedure: Dilute NaI in acetone is added to the sample
and shaken. If no precipitate forms after 5 minutes, place
the test tube in a 50oC water bath
Positive test: The formation of a white precipitate indicates
the presence of halides

32
 Polymers (Macromolecules)
 A polymer is a large (high mw) molecule made by
linking together smaller units called monomers
eg: Polystyrene is a polymer consisting of styrene
monomers

Classification of chain structure

The polymer chain can have the following chain
structures:

33
Classification of polymer sequence
 Homopolymers have identical repeating monomers
(identical sequence):

 Copolymers have different repeating monomers, thus

they may have different sequences:

Naming polymers
A polymer is often named according to the monomer that
was used to form it (but some have trade names)
Examples:

34
Polymerization reactions (formation of polymers)
 Chain polymerization (aka Addition polymerization)
occurs in a multi-step process involving the initiation,
propagation and termination steps
The monomers involved must have a C=C (C double
bond) and the polymer formed has the same atoms as
the monomers
eg. Polystyrene and polyvinylchloride (PVC)
 Initiation step: An initiator is added to form a free radical
which reacts with a monomer to start a growing chain
 Propagation step: The growing chain reacts with more
monomers resulting in an increase in chain length
 Termination step: Two growing chains react resulting in
an ‘unreactive’ or ‘dead’ polymer

35
 Chain polymerization of polyvinyl chloride:

 Stepwise polymerization (aka Condensation polymer-

ization) occurs when monomers link together by
eliminating a small stable molecule
The monomers involved must have two reactive end
groups
eg. Nylon (joined together by amide links) and
Polyester (joined together by ester links)
Step polymerization of Nylon 6,6 (water is eliminated):
n(H2N-(CH2)6-NH2) + n(HOOC-(CH2)4-COO)
Hexamethylamine Adipic acid

H-(NH-(CH2)6-NH-CO-(CH2)4-CO)n-OH + H2O
Nylon 6,6

36
Crystalline and amorphous polymers
 Amorphous polymers lack ordered molecular structure
When heated, they soften over a wide temperature
range known as the glass transition temperature, Tg
Examples: polystyrene and poly(methyl methacrylate)
 Crystalline polymers have ordered molecular structure
They have melting points, Tm (the temperature at which
the ordered regions break
Examples: polyethylene, PET polyester
 Liquid crystals are polymers that show intermediate
phases (subject actively researched in both industry
and academia)
Major polymer types:
 Fibers have strong forces between the polymer
chains and the chains are lined up by stretching
 Plastics have moderate forces between the polymer
chains and are classified as follows:
Thermoplastics soften when heated and can be
reshaped (eg chain polymers, polyesters and nylons)
Thermosets do not soften when heated but becomes
harder as they become more crosslinked
 Elastomers have weak forces between the polymer
chains and their shapes are maintained by
crosslinking
37
 Drawing Isomers
Structural (constitutional) isomers
Hydrocarbons
Question: Draw and name the isomers of C5H12
Answer:

Alcohol and ether

Question: Draw and name the isomers of C2H6O
Answer:

Alkyl halide
Question: Draw the two isomers of C2H4Cl2
Answer:

38
Aromatic hydrocarbon
Question: Draw all the isomers of hydroxybenzoic acid
Answer:

Stereoisomers (geometric isomers)

Question: Draw the geometric isomers of C2H2Br2
Answer:

39
Question: Draw the stereoisomers of 1,2-dimethyl
cyclobutene
Answer: The structure of 1,2-dimethyl cyclobutene is

The stereoisomers of the molecule are

Optical isomers
Question: The CH3CHClBr molecule is optically active
(rotates the plane of polarized light). Determine the
chiral center and draw the enantiomers of the molecule
Answer: The chiral center is the carbon atom that has
four different groups attached to it (*)
The enantiomers of the molecule is given as follows:

L-configuration D-configuration

40