Organic Chemistry

Shahid Uz Zaman
Lecturer, Department of Chemistry
Bangladesh University of Engineering and Technology (BUET)

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 Syllabus
Organic Chemistry 3.00 Credit (3 hrs/wk)
The hybridization of carbon atom and covalent bonding.
A comprehensive study of aliphatic hydrocarbons with special reference to
nomenclatures, method of preparation, properties and important uses.
Types of reactions of aliphatic hydrocarbons and their industrial
applications.
Structure, nomenclature, preparation, properties, reactions and industrial
applications of aliphatic hydrocarbon homologues.
Aromatic compounds and aromaticity. Preparation, properties, reactions
and industrial applications of benzene and its derivatives. Heterocyclic
compounds and their applications. Basic concepts of organic dyes.
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 Distribution of
Marks
Class Participation 10%

Continuous Assessment 20%

Final Examination 70%

Total 100%

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 Lecture Plan: Shahid Uz
Zaman
Lecture Topics
IUPAC Nomenclature of alkanes, alkenes, alkynes, alkyl halide, alcohol, amines,
L1 carsbonyl compounds and carboxylic acids
Constitutional Isomers and Stereoisomers, Enantiomers and Chiral Molecules,
L2 Naming Enantiomers: The R,S-System
Chirality, Fischer Projection Formulas, Stereoisomerism of Cyclic Compounds,
L3 Separation of Enantiomers and Resolution
Conformations, physical properties of alkanes,
L4
Preparation and chemical reactions of alkanes, Industrial uses of alkanes
L5
Class test-1
L6
Physical properties of alkenes, preparation of alkenes from dehydrhalogenation of
L7 alkyl halides, dehydration of alcohols and reduction of alkynes.

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 Hydrogenation of alkenes, addition reactions of alkenes with hydrogen halides, sulfuric
L8 acid and water

Oxymercuration–Demercuration reaction and hydroboration–oxidation reaction of alkenes,

L9 oxidations of alkenes

Physical properties, preparation and reactions of alkynes

L10

Introduction of alkyl halides, types of alkyl halides, physical properties and preparation of
L11 alkyl halides

Nucleophilic Substitution Reactions: Nucleophiles, Leaving Groups, Kinetics of substitution

L12 reaction and it’s mechanism.

Elimination Reactions of Alkyl Halides and it’s mechanism; properties , synthesis and reaction
L13 of alcohols,

Class test-2
L14

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 Synthesis and reactions of ethers. Industrial applications of alcohols and ethers.
L15

Properties, synthesis and reactions of amines

L16

Claisen Condensation, Aldol Reactions, Crossed Aldol Condensations; properties and synthesis of
L17 aldehydes and ketones

Physical properties, preparation and applications of Carboxylic Acids and their derivatives
L18

IR Spectroscopy
L19

NMR Spectroscopy for organic compounds

L20

NMR Spectroscopy for organic compounds

L21

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 Reference
Books
Organic Chemistry by G. Solomons
Organic Chemistry by Morrision & Boyd
Organic Chemistry by I.L. Finar, vol. 1 & 2

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 Dealing with Organic Formulas and
Structures
1. Condensed Structural Formula: Shows how the atoms
are grouped together
2. Line Structure: Represents the chain as a zig-zag line

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 Nomenclature

• International Union of Pure and Applied Chemistry

(IUPAC) has established the system
• We will refer to names derived from this system as
systematic nomenclature or IUPAC nomenclature
• Additional names such as isopentane and neopentane
are common names
• A compound may have more than one name BUT a
name must specify only one compound

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 Alkanes - Nomenclature

The name of every organic molecule has 3 parts:

1. The parent name indicates the number of carbons in the longest
continuous chain.
2. The suffix indicates what functional group is present.
3. The prefix tells us the identity, location, and number of substituents
attached to the carbon chain.

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 Alkanes - Nomenclature

Parent – Longest straight carbon chain

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 Alkanes - Nomenclature
Suffix – Our first functional group is alkane, so the suffix is –ane
For later functional groups we will drop the –ane root suffix for others
Alkane chain # Carbons Name
CH4 1 methane
CH3CH3 2 ethane
CH3CH2CH3 3 propane
CH3CH2CH2CH3 4 butane
CH3CH2CH2CH2CH3 5 pentane
CH3CH2CH2CH2CH2CH3 6 hexane
CH3CH2CH2CH2CH2CH2CH3 7 heptane
CH3CH2CH2CH2CH2CH2CH2CH3 8 octane
CH3CH2CH2CH2CH2CH2CH2CH2CH3 9 nonane
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3 10 decane
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3 11 undecane
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2C 12 dodecane
H3
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 Alkanes - Nomenclature
Prefix – Our substituents will be branches in the alkane structure
A branch is another alkane minus one hydrogen – an alkyl group
Example – if CH3- is a branch on a longer chain:

CH3- is CH4 minus 1 hydrogen

Since it is a side chain we will replace the –ane suffix with –yl

CH3- is a methyl group

We can also abbreviate this group as Me-

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 Alkanes - Nomenclature
Prefixes -
Alkyl group Structure IUPAC name Abbreviation

CH3- CH3- methyl Me-

CH3CH2- ethyl Et-

CH3CH2CH2- n-propyl n-Pr

CH3CHCH3 isopropyl or i-propyl i-Pr

CH3CH2CH2CH2- n-butyl n-Bu

CH3CH2CHCH3 sec-butyl s-Bu

(CH3)2CHCH2- isobutyl or i-butyl i-Bu

(CH3)3C- tert-butyl or t-butyl t-Bu

C6H5- phenyl Ph

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 Alkanes - Nomenclature

1. Find the parent carbon chain and add the suffix.

Note that it does not matter if the chain is straight or it bends.

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 Alkanes - Nomenclature

2. Also note that if there are two chains of equal length, pick the chain
with more substituents.
In the following example, two different chains in the same alkane have
seven C atoms. We circle the longest continuous chain as shown in the
diagram on the left, since this results in the greater number of
substituents.

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 Alkanes - Nomenclature

3. Number the atoms in the carbon chain to give the first substituent the
lowest number.

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 Alkanes - Nomenclature

4. If the first substituent is the same distance from both ends, number the
chain to give the second substituent the lower number.

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 Alkanes - Nomenclature

5. When numbering a carbon chain results in the same numbers from either end of
the chain, assign the lower number alphabetically to the first substituent.

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 Alkanes - Nomenclature

6. Combine substituent names and numbers + parent and suffix.

• Precede the name of the parent by the names of the substituents.

• Alphabetize the names of the substituents.
• Precede the name of each substituent by the number that indicates its
location.
• Separate numbers by commas and separate numbers from letters by
hyphens.
• The name of an alkane is a single word, with no spaces after hyphens
and commas.

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 Alkanes - Nomenclature

Combine substituent names and numbers + parent and suffix.

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 Alkanes - Nomenclature

Cycloalkanes are named by using similar rules, but the prefix

cyclo- immediately precedes the name of the parent.

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 Alkanes - Nomenclature
1. Find the parent cycloalkane.

2. Name and number the substituents. No number is needed to indicate

the location of a single substituent.

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 Alkanes - Nomenclature

For rings with more than one substituent, begin numbering at one
substituent and proceed around the ring to give the second substituent
the lowest number.

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 Alkanes - Nomenclature
With two different substituents, number the ring to assign the lower
number to the substituents alphabetically.

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 Alkanes - Nomenclature
Note the special case of an alkane composed of both a ring and a long
chain. If the number of carbons in the ring is greater than or equal to
the number of carbons in the longest chain, the compound is named as a
cycloalkane.

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Alkanes - Nomenclature

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Practice

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 Other Functional Groups - Nomenclature

The IUPAC rules for all other functional groups will differ only by the following:
1. Suffix will change to reflect functional group
2. Some functional groups have priority over others
3. For now: alcohol > alkyne > alkene > alkane=alkyl halide
4. The longest chain must contain the suffix functional group – even if not
the longest chain overall
5. Numbering gives this functional group the lowest number – even if there
are other groups that would be lower
6. If an alkene has stereochemistry, it must be specified in the prefix

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30
Alkyl Halides - Nomenclature

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Alcohols - Nomenclature

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 Alcohols - Nomenclature

• When an OH group is bonded to a ring, the ring is numbered beginning

with the OH group.
• Because the functional group is at C1, the 1 is usually omitted from the
name.
• The ring is then numbered in a clockwise or counterclockwise fashion to
give the next substituent the lowest number.

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 Alcohols - Nomenclature

• Compounds with two hydroxyl groups are called diols or

glycols.
• Compounds with three hydroxyl groups are called triols.

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Ethers

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Ethers

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Alkenes - Nomenclature

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 Alkenes - Nomenclature

• Compounds that contain both a double bond and a hydroxy group are
named as alkenols and the chain (or ring) is numbered to give the OH
group the lower number.

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 Alkenes - Nomenclature
• Compounds with two double bonds are named as dienes by changing
the “-ane” ending of the parent alkane to the suffix “-adiene”.
• Compounds with three double bonds are named as trienes, and so forth.
• In naming cycloalkenes, the double bond is located between C1 and C2,
and the “1” is usually omitted in the name.
• The ring is numbered clockwise or counterclockwise to give the first
substituent the lower number.

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40
 Conformation and configuration
Configuration is a fixed stereochemical property of compounds. Unlike conformation, a change
in configuration requires bonds to be broken and formed. Any molecule has a limited number of
configurations in which it can exist.

Alkenes can exist in two configurations, for example but-2-ene may have the terminal methyl groups
in a trans (across from each other) or cis (on the same side) position:

H3C H H3C CH 3

trans-but-2-ene C C cis but-2-ene C C

H CH 3 H H

Changing trans butadiene into cis- butadiene (or vice versa) requires the breaking, and
subsequent reforming, of the p bond. This is a high- energy process and does not take place
at room temperature. At room temperature, but-2-ene (and other alkenes) can be physically
separated into the two pure isomers.
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Stereochemical Configurations of Alkenes:
Z/E Designations
There are limitations to cis and trans alkene designations.

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Stereochemical Configurations of Alkenes:
Z/E Designations
continued…

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The configuration of an alkene can be obvious in some cases (such as but-2-ene) however in others it is not, for example
is the molecule below a cis or trans alkene?

H3C H2C CH 3

C C
H CH 3

In order to provide an unambiguous means for assigning configuration to alkenes and also to chiral centres , organic
chemists have adopted the ‘Cahn-Ingold-Prelog’ (CIP) rules for configurational assignment.

These are simple to use - first one assigns a ‘priority’ to each group attached to each carbon atom at each end of the
alkene. Z (from the German zusammen, together) or E (from the German entgegen, across):

High Low High

High
Z alkene: C C E alkene: C C

Low Low High Low

(relative priorities are of a group on a C atom to its partner on the same atom)

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The CIP priority rules are defined as follows, in their own order of priority:

a) Atoms of higher atomic number have priority:

H3C CH 3 High High

e.g. C C C C

H H H H

In this molecule the attached carbon atoms at each end of the double bond
have priority over the attached H atoms, hence this is a Z alkene

b) When the attached atoms are identical on each side, isotopes of higher mass have priority

D High High
H3C
e.g. C C C C

H H H H

In this molecule the attached carbon and deuterium (deuterium is the H-2 isotope)
atoms at each end of the double bond have priority over the attached H atoms, hence
this is a Z alkene

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The CIP priority rules are defined as follows, in their own order of priority:

a) When the atoms and isotopes attached on each side are identical, move out until a point of difference is encountered and
apply the following rules:

a) Priority goes to the group with the element of highest atomic number at the point of difference .

H H2C NH 2 Low High

e.g. C C C C

H3C C CH 3 High Low

H3C CH 3 E alkene

b) Priority goes to the group with the highest sum of atomic numbers if the atoms are of the same types at the point of
difference. In the example below, the point of difference on the right hand side is two carbons away from the alkene
carbon atom
CH 3
H H2C CH Low High
CH 3
e.g. C C C C

H3C H2C CH 2 High Low

H2 E alkene
H2C C
CH 3

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Imagine you are moving out from the C tothe adjacent atoms. Going both up (to C1) and down
(to C1') leads to a CH2 group, i.e. no difference. Moving to the next atom reveals that C2 (top
branch) is attached to C,C,H but that C2' (lower branch) is attached to C,H,H. The upper branch has
the highest sum of attached atomic numbers and therefore has priority.

1 2 CH 3
H H2C CH
CH 3 Upper: C-> C1(C,H,H) -> C2(C,C,H) Low High
C C  2' C C
H3C H2C CH 2
H2 Lower: C-> C1(C,H,H) -> C2(C,H,H) High Low
1' H2C C E alkene
CH 3

There is one more rule:

d) In the case of double and triple bonds, ‘dummy’ atoms should be added and counted in the determination of priority.
See next slide.

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Here is an example of the determination of configuration for an alkene attached to a double bond:

C C <--dummy atoms
1 2
1 2
H CH CH 2 Upper: C-> C1(C,C,H)
H HC CH 2
C C  2'
C C  2'
H3C H2C CH 2
H3C H2C CH 2 H2 Lower: C-> C1(C,H,H)
H2 1' H2C C
1' H2C C
CH 3
CH 3

Low High

C C
High Low
E alkene

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Alkenes - Nomenclature

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 Alkynes - Nomenclature

• Alkynes are named in the same general way that alkenes are
named.

• In the IUPAC system, change the –ane ending of the parent alkane
name to the suffix –yne.

• Choose the longest continuous chain that contains both atoms of the
triple bond and number the chain to give the triple bond the lower
number.

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 Alkynes - Nomenclature

• Compounds with two triple bonds are named as diynes, those with
three are named as triynes and so forth.
• Compounds with both a double and triple bond are named as
enynes.
• The chain is numbered to give the first site of unsaturation (either
C=C or CC) the lower number.

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Practice

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