CHEM 171 CHEMICAL REACTIVITY

ORGANIC CHEMISTRY

Dr.V. Paideya
2021

University of KwaZulu Natal School of

Chemistry and Physics
 Learning Objectives
 Recognize Stereochemistry. Classify molecules as chiral or achiral, identify
chiral carbons as (R) or (S), identify:
 relationships between pairs of molecules as enantiomers, diastereomers, or
equivalent, and
 identify when a solution is racemic versus optically active.
 Apply Stability-Reactivity Principles. Predict, explain, and rank the relative
speeds of different chemical reactions
by applying structure-dependent patterns in stability
combined with application of mechanism recognition.
 Recognize Structure Relationships Between Chemicals. Be able to recognize
relationships between two chemical structures as :
 the same structures,
 resonance structures,
 structural isomers,
 enantiomers, or
 diastereomers.

2
 ISOMERS
Two types: (a) Structural isomers (b) Stereoisomers
(a) Structural isomers
 Molecules with the same chemical formula but different
bonds between the atoms
Now called... CONSTITUTIONAL ISOMERS
 Constitutional isomers have different properties:
e.g. butane (C4H10) has 2 structural isomers
These are…..?
n-Butane: C4H10 2-methylpropane: C4H10
CH3 CH2 CH2 CH3 CH3 CH CH3 bp = -12 °C
bp = 0 °C mp = -138 °C mp = -159 °C
CH3 3
 Example
How many constitutional isomers are formed from C5H12?
Draw their structures.
Solution: THREE CONSTITUTIONAL ISOMERS
1) CH3 CH2 CH2 CH2 CH3 2) CH3 CH CH2 CH3
CH3
n-pentane 2-methylbutane

3) CH3
CH3 C CH3
CH3 2,2-dimethylpropane
4
 CONSTITUTIONAL (STRUCTURAL) ISOMERS

The general formula for ALKANES is…... C n H 2n 2

n = 1, 2 and 3 1 ISOMER
 The number of ISOMERS
n=4 2 ISOMERS
increases with n…..
n=5 3 ISOMERS
n=6 5 ISOMERS
n=7 9 ISOMERS
n = 40
62,491,178,805,831 ISOMERS n=8 18 ISOMERS
n=9 35 ISOMERS
HOMEWORK: n = 10 75 ISOMERS
DRAW THE ISOMERS OF C40H82 !!!
n = 20 366,319 ISOMERS
5
Constitutional isomers for multibonds
Example: Alkene
C6H10
(E,E)-2,4-hexadiene

(E)-1,3-hexadiene

(Z,Z)-2,4-hexadiene
(Z)-1,3-hexadiene

(Z,E)-2,4-hexadiene
1,5-hexadiene 6
 Constitutional isomers for multibonds
Example: Alkyne
C6H6
H3C C C C C CH3

2,4-hexadiyne
hexa-2,4-diyne
CH3
H C C C C CH2

1,3-hexadiyne
hexa-1,3-diyne

7
 OPTICAL ISOMERISM

 Optical isomerism arises when molecules have a

structure such that the mirror image is not
superimposable on the original molecule.

 occurs whenever there are four different groups

bound to the same tetrahedral carbon atom.

Some terminology…….

8
 OPTICAL ACTIVITY IN ORGANIC
COMPOUNDS
 Stereogenic centre has four different groups attached
to a tetrahedral carbon atom

Stereogenic W Chiral carbon

centre atom
C*
Z
X
Y
 The carbon involved is called a chiral carbon or
stereogenic carbon and the molecule is known as a chiral
molecule.
9
Example: 2-butanol
 Perspective formula
Wedge-dash notation
2-Butanol
Dash shows bond going Simple line for
backwards from the viewer Bonds aligned to
OH the asymmetric
center in the plane

C*
H3C
CH2CH3
H
Solid wedge represents a
bond extending out Chiral centre
towards the viewer
10
 Fischer projection
2-Butanol
Bond going Bonds aligned to
backwards from CH3 the asymmetric
the viewer center in the plane

HO * CH2CH3
Bond extending
out towards the
viewer H
Chiral centre

11
ENANTIOMERISM in ORGANIC CHEMISTRY
• 2-butanol has two optical isomers.
• A pair of isomers called enantiomers -
(non-superimposable mirror images of each other)

View in 3-D
“mirror” View in 3-D

OH OH

C C
H3C
CH2CH3 CH3CH2 CH3
H H

Chapter 22.3: 3rd Edition

 Question
Identify the chiral carbon (stereogenic centre) and draw the
structural formula for each of the following molecules:
(a) 1-chloroethanol (b) 2,3,5-trimethylhexane
(c) Methylcyclohexane (d) 1,3-dimethlycyclopentane
Solution
(a) 1-chloroethanol (b) 2,3,5-trimethylhexane

(c) methylcyclohexane (d) 1,3-dimethlycyclopentane

13
 NAMING OPTICAL ISOMERS
 Stereogenic centre creates two molecular optical isomers
Two
Cl Cl
configurations
C* *C Enantiomers
H H
OH
HO CH3
H3C

How do we name these isomers??

Solution: Use R-S nomenclature system for designating
the configuration
We assign priorities as in the E, Z system……...
14
CAHN-PRELOG-INGOLD R,S-NOMENCLATURE
1. Assign relative priorities to each of the four groups on
the stereogenic carbon to describe the configuration.

The priorities are given by rules:

• Higher atomic numbers are given higher priorities.

• If necessary, the second atom in each substituent is

used to determine the priorities.

Chapter 23.5: “Chemistry: The Central Science: A Broad Perspective” 3rd Edition
 CAHN-PRELOG-INGOLD R,S-NOMENCLATURE
2. Draw the molecule with the lowest-priority group
pointing directly into the page….

and the other three groups pointing out of the page in an

arrangement like a steering wheel or Mercedes-Benz symbol

Example: 2-Butanol….. C
OH
CH3 C CH2 CH3
H
Draw molecule as a wedge and dashed line diagram
 Chapter 23; pg. 940.
2- butanol OH
“Chemistry: The Central Science:
A Broad Perspective” 3rd Edition.

CH3 C CH2 CH3

OH H OH

H C C
H
CH2CH3 H3CH2C
H3C CH3

DO NOT FORGET THE OTHER ISOMER……….

THESE ARE THE TWO…. ENANTIOMERS
...or ....OPTICAL ISOMERS
17
2- butanol OH 1. Assign priorities:
O > CMe = CEt > H
C
H
CH2CH3 C,H,H > H,H,H
CH3
CEt > CMe

18
 1 OH 2-Butanol
1. Assign priorities to each group:
4 H C 2
CH2CH3 O > CEt > CMe > H
CH3
3

1 OH
2. Redraw the molecule with the
C 2 lowest priority group facing in.
H3C CH2CH3
3
Now what?????

19
 1
OH 2-Butanol

C 2
H3C CH2CH3
3
(R)-2-Butanol

3. Look at the direction in which the priorities decrease.

 If they decrease in a clockwise direction, the
stereogenic centre is called “R” or rectus

which is Latin for “right.”

Or….
20
 1
OH 2-Butanol

2 C 3
CH3CH2 CH3
(S)-2-Butanol

 If the priorities decrease in a counter-clockwise

direction the stereogenic centre is called “S” or
sinister, which is Latin for “left.”

21
Example: What are the configurations of the following
chiral molecules?

NH2
N > CEt > CMe > H NH2

C C
H H3C
CH2CH3 CH2CH3
CH3 H

1 2 3 2

H2N CH2CH3 H3C CH2CH3

C C

A22
3 CH3 1 NH2
Example: Give the configuration of the stereogenic
centre in each of the following molecules:
Cl
CH2OH

C H C
H
C OH CH2OH
HO C
Cl
O O
(A) (B)

2-chloro-3-hydroxy-propanoic acid

THEY LOOK DIFFERENT BUT ARE THEY???

23
A) 1. Assign priorities to each group:
CH2OH
Cl > Calc = Ccarb > H
C
H
C OH
Cl
O Go to next atoms on tied carbons

O,O,O > O,H,H

Ccarbox > Calc

Cl > Ccarb > Calc > H

24
 3
A) CH2OH 1. Assign priorities to each group:

4 C 2
Cl > Ccarb > Calc > H
H
C OH
Cl
1 O

2. Redraw the molecule with the

3 CH2OH
lowest priority group facing in.

C 2 3. Look which way the priorities

Cl C OH decrease.
1
O

The priorities decrease anti-clockwise, so this centre is “S”

(S)-2-chloro-3-hydroxy-propanoic acid
25
B) 1 Cl
1. Assign priorities to each group
4
H C 3 Cl > Ccarb > Calc > H
CH2OH
HO C
2 2. Redraw the molecule with the
O lowest priority group facing in.
1 Cl
3. Direction of the priorities
C decrease?
HO C CH2OH
2  The priorities decrease anti-
O 3
clockwise, so this centre is “S”

(S)-2-chloro-3-hydroxy-propanoic acid
Example: Give the configuration of the stereogenic
centre in each of the following molecules:

CH2OH Cl
A) B)
C H C
H
C OH CH2OH
Cl HO C
O
O
2-chloro-3-hydroxy-propanoic acid

THEY LOOK DIFFERENT BUT ARE THEY???

WE JUST FOUND OUT THAT THEY ARE IDENTICAL!!!!!
27
WHAT IF?????
 If we flip the COOH and H ???????

A) CH2OH A’) CH2OH

C C
H HO C H
C OH
Cl O Cl
O
3 CH2OH 3 CH2OH

C 2 C
Cl 1
1
C OH HO C Cl
2
O O
“S” configuration “R” configuration 28
 EXAM QUESTION

What is the structural formula of (R)-2-chloro-2-butanol?

Hint: Make use of perspective formula or dash-wedge notation.

Solution: DRAW MOLECULAR STRUCTURE

OH
H3C C CH2 CH3
Cl

ASSIGN PRIORITIES ??
29
 CHCH *** ***
3 3 CH
CHCH CHCHCH
33
CH3 CH CH CH3
BrBr ClCl
[2R,3R] [2S,3S] Br Cl [2R,3S] [2S,3R]
a CH CH33 b CHCH33 c CH
CH33 d CHCH33
R RCH3 S SCH3 R R CH3 S SCH3
BrBr RCC HH HHSCC BrBr BrBrR CC HH HHSCC BrBr
Br C H H C Br Br C H H C Br
HH CC ClCl ClCl CC HH ClCl CC HH HH CC ClCl
HRRC Cl ClS S C H Cl S SC H HR RC Cl
RCH
CH SCH
CH SCHCH RCH
CH
33 33 33 33
CH3 CH3 CH3 CH3

enantiomeric pairs enantiomeric pairs

• Enantiomeric pair differ only in optical activity

Chapter 23.6, page 940: “Chemistry: The Central Science: A Broad Perspective”
30
Diastereomers
CH3 *CHa &CH
*cb &CHc 3
Br Cl b &d
a & d
a CH3 b CH3 c CH3 d CH
3
R S R S
Br C H H C Br Br C H H C Br
H C Cl Cl C H Cl C H H C Cl
R S S R
CH3 CH3 CH3 CH3
 Diastereomers - are distinct chemical compounds,
differing not only in optical activity but also in mp, bp.,
, solubility etc…
 molecule with n stereogenic centres may exist in
maximum of 2n stereisomeric forms, with maximum of
2n/2 enantiomeric pairs 31
 O O
Meso compound
* *
HOC CH CH COH
OH OH

CO2H CO2H CO2H CO2H

R S R S
H C OH HO C H H C OH HO C H
HO C H H C OH H C OH HO C H
R S S R
CO2H CO2H CO2H CO2H
O O O
170
Enantiomeric 170 °CC 170
170 °CC 140
140 °CC Meso
pairs O
+12+12° O
-12°
-12 0O
0° compounds

 meso compound - an achiral (optically inactive)

diastereomer of compound with stereogenic centres
 arises because 4 different groups making each of C-2 & C-3
stereogenic are same 4 different groups…(!) 32
Meso compound

CO2H CO2H CO2H CO2H

R S R S
H C OH HO C H H C OH HO C H
-------------------- -------------------- -------------------- --------------------
HO C H H C OH H C OH HO C H
R S S R
CO2H CO2H CO2H CO2H

Enantiomers, Chiral Identical, achiral, Meso form

 possess plane of symmetry bisecting central C-C bond

33
 Newman projections
 Shows arrangements in space e.g. Ethane C2H6
H 60°
H
 Staggered H H H H H
H H
conformation
H
H H H H
H H H
H
“dash-wedge” “sawhorse” Newman

 Eclipsed H
H 0°
H HH
conformation H
H H
H H H
H H
H H
H H H
“dash-wedge” “sawhorse” Newman34
 Cyclohexane conformations
a a
a a 5 a e 1
e 6
e a 5
1
6 e "flip" 3 e
e e 4 a 2 e
3
e 2 a 4 e e
e a a
a a
Chair conformations
H H
H H H
H
H H H
Cyclohexane H
H H
Boat conformation 35
 Examples
1,2-Dimethylcyclopentane

H H
H CH3 CH3 H CH3
H H H
H H
H H H H

H H H CH3

Cis-1,2-Dimethylcyclopentane Trans-1,2-Dimethylcyclopentane

36
 Summary of Hart et al. “Organic Chemistry: A Short
Course” 12th Edition, page 52-54
isomerism
Different bond
Structural
pattern (constitutional)
isomer
isomers
Same bond
pattern
Stereoisomer

Interconvertible by Not interconvertible

single bond rotation by bond rotation

Conformers Configurational
(rotamers) isomers
37
 Exercise
1. Draw the structures of
a) (Z)-3-methyl-2-pentene c) (E,Z)-2,4-heptadiene
b) (S)-2-bromopropan-1-ol d) (2S,3R)-3-bromobutan-2-ol

2. Using the Newman projection draw the structure of a

staggered conformation of butane.

3. Using the Fischer projection draw a structure of

(S)-2-methylpentanoic acid.
4. Draw the structure for the cis- and trans-isomers of
1-bromo-2-chlorocyclopropane 38