Che 220: Stereochemistry: Chirality & Enantiomers

CHE 220: STEREOCHEMISTRY LECTURE 2
Chirality & Enantiomers

D.M. Shadrack (Chem Dept-SJUT)
Wednesday, February 01, 2012 D.M. Shadrack (Chem Dept-SJUT) 1
Chirality and Enantiomers
The left and right hands are mirror image and nonsuperimposable
Chirality, what does it mean? Chiral mean handedness.

Chirality and Enantiomers, cont..,

Chirality: Is ability of molecule to exist in two non superimposable mirror-image forms. Note, The effects of chirality give rise to Enantiomerism Enantiomer: molecules that are nonsuperposable mirror images
Chiral molecule
What is a chiral molecule?

Chiral molecule
Definition A molecule that is non superposable mirror image. Note, Non-superimposability on the mirror image is a necessary and sufficient condition for chirality; no exception has ever been found
Chiral molecule, cont..,

A molecule is said to be chiral if it lacks symmetry and its mirror images are not superimposable. To be chiral a molecule must lack symmetry, that is, a chiral molecule can not have any type or symmetry.
Chiral center
Fig A
Also known as stereogenic center , stereocenter or chiral carbon. The asterisk (*) indicate the stereocenter carbon.
Look at fig A & B, then, What is a chiral center?

Wednesday, February 01, 2012 D.M. Shadrack (Chem Dept-SJUT)
*
OH
Fig B
7
Chiral center, cont..,

Is a centre of asymmetry in a molecule, that is, the carbon atom that has FOUR different atoms attached to it. Other examples
Wednesday, February 01, 2012
Achiral molecules Are stereoisomers that are superimposable on its mirror image due to plane of symmetry though may possess chiral centers. (e.g most of the socks).
Generally,
10
Practice problem
Which of the following compounds would form enantiomers because the molecule is chiral?
11
Practice problem - answer

The second carbon atom in 2-bromo-2methylbutane contains two identical CH3 substituents. As a result, this compound is achiral and does not form enantiomers.
12
The second carbon atom in 1-bromo-2methylbutane carries four different substituents: H, Br, CH3, and CH2CH3. As a result, this molecule is chiral and it forms enantiomers.
13
Test for chirality

Plane of symmetry (or Mirror plane): Is an imaginary line that bisects the molecule such that the two halves are mirror image of each other.
A molecule will not be chiral if it possesses a plane of symmetry

Test for chirality, cont..,

All molecules with plane of symmetry are achiral. For example.
H3C H3C
Cl C2H6 H3C H
Cl
2-Chloropentane has a plane of symmetry

2-Chlorobutane does not posses a plane of symmetry

15
Test for chirality, cont..,

line of symmetry Br *C *
Br H CH3 H H3C CH3 H H3C
Br C
*
Br
Mirror
16
Below are the examples of superposable and nonsuperposable molecules

CH3 CH3
=
C
CH3CH2 CH3CH2CH2
CH2CH3 CH2CH2CH3
3-Methylhexane
Mirror 3-Methylhexane and its mirror image
17
=
C CH3CH2 CH3CH2
CH3
CH3
CH2CH3 CH2CH3
3-Methylpentane Mirror 3-Methylpentane and its mirror image
18
Now,
For the case of 3-Methylpentane (above), rotating a molecule at 180o the molecule will be superimposed (= identical). Unlike 3-Methylhexane no superimposition (= chiral molecule)
Note:1. A molecule with one chiral C atom has two enantiomers, two molecules that are each other's mirror image. There are many molecules in nature with more than one chiral C atom, glucose, cholesterol, prostaglandins to name a few. Each chiral C atom adds another two enantiomers to the total number of possible compounds.
In other words, the answer to the question, how many different compounds exist when there are n chiral centers combined in one molecule, is 2n.
21
NOTE 2,
Presence of one chiral center in compound is a sufficient condition for chirality , but the presence of more than one chiral center in compound is NOT a sufficient condition to cause chirality (compound be a chiral). Some chiral molecules do not possess chiral centers, hence chiral center is not a necessary condition for chirality.
Physical properties of Enantiomers

Have identical physical properties (e.g. melting point, boiling point, solubility etc.) except for optical activity. They are also identical in chemical reactivity (except with chiral reagents or chiral catalysts). Pair of enantiomers can be distinguished by their optical activity.
Optical Activity
The rotation by a molecule of the plane-polarized light Plane polarized light: is a light which travel only in one plane. Ordinary light is in a wave motion oscilating in all planes.
Optical Activity, cont..,

Example
light end view of plane of oscilation
25
Polarimeter
Is a device to measure optical activity Or Is an instrument that determine the plane of polarization.
Thursday, March 08, 2012 D.M. Shadrack (Chem Dept-SJUT) 26
Thursday, March 08, 2012
27
Principal parts of polarimeter

Source of light (lamp) A polarizer: Is the lense made up of cystaline material like Nickel prism. i.e special crytaline with CaCO3/calcite. It acts as a filter. Sample tube Analyzer (lense no. 2) Scale (in degree)
Thursday, March 08, 2012
28
Specific rotation
The observed rotations () of enantiomers are opposite in direction. One enantiomer will rotate polarized light in a clockwise direction, termed dextrorotatory or (+), and its mirror-image partner in a counterclockwise manner, termed levorotatory or ().
The prefixes dextro and levo come from the Latin dexter, meaning right, and laevus, for left, and are abbreviated d and l respectively. If equal quantities of each enantiomer are examined, using the same sample cell, then the magnitude of the rotations will be the same, with one being positive and the other negative. Hence, Dextrorotatory (+) or (d) and Levorotatory (-) or (l)
Angle of rotation, o
Angle of rotation, o depends on; (i) wave length of light (ii) Temperature (iii) concentration (iv) length of sample tube (v) solvent e.g CH2Cl2
31
Angle of rotation, o
In order to place measured rotation on a standard basis chemists calculate a quantity called the specific rotation *+.
That is, Specific rotation,

t D
l.c
32
Where,
*+ = Specific rotation = the observed rotation l = length of sample tube in decimeters (1 dm = 10 cm) c = the concentration of the the solution in g/ml of solution or density in g/mL for neat liquids t = temperature D = wave length of sodium lamp ( = 599.6 nm).
Practice problems
Problem 1: enantiomers and chirality
Problem 2: chiral and achiral molecules

Problem 3: specific rotation
Problem 4: diastereomers The Origin of optical Activity (GO AND READ)


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CHE 220: STEREOCHEMISTRY LECTURE 2

Chirality & Enantiomers

Chirality and Enantiomers

Chirality, what does it mean? Chiral mean handedness.

Chirality and Enantiomers, cont..,

What is a chiral molecule?

Chiral molecule, cont..,

Look at fig A & B, then, What is a chiral center?

Chiral center, cont..,

Wednesday, February 01, 2012

D.M. Shadrack (Chem Dept-SJUT)

Wednesday, February 01, 2012

D.M. Shadrack (Chem Dept-SJUT)

Wednesday, February 01, 2012

D.M. Shadrack (Chem Dept-SJUT)

Practice problem - answer

Wednesday, February 01, 2012

D.M. Shadrack (Chem Dept-SJUT)

Wednesday, February 01, 2012

D.M. Shadrack (Chem Dept-SJUT)

Test for chirality

A molecule will not be chiral if it possesses a plane of symmetry

Test for chirality, cont..,

2-Chloropentane has a plane of symmetry

2-Chlorobutane does not posses a plane of symmetry

D.M. Shadrack (Chem Dept-SJUT)

Test for chirality, cont..,

Wednesday, February 01, 2012

D.M. Shadrack (Chem Dept-SJUT)

Below are the examples of superposable and nonsuperposable molecules

Mirror 3-Methylhexane and its mirror image

Wednesday, February 01, 2012

D.M. Shadrack (Chem Dept-SJUT)

3-Methylpentane Mirror 3-Methylpentane and its mirror image

Wednesday, February 01, 2012

D.M. Shadrack (Chem Dept-SJUT)

Wednesday, February 01, 2012

D.M. Shadrack (Chem Dept-SJUT)

Physical properties of Enantiomers

Optical Activity, cont..,

light end view of plane of oscilation

Wednesday, February 01, 2012

D.M. Shadrack (Chem Dept-SJUT)

Thursday, March 08, 2012

D.M. Shadrack (Chem Dept-SJUT)

Principal parts of polarimeter

Thursday, March 08, 2012

D.M. Shadrack (Chem Dept-SJUT)

Wednesday, February 01, 2012

D.M. Shadrack (Chem Dept-SJUT)

That is, Specific rotation,

D.M. Shadrack (Chem Dept-SJUT)

Problem 2: chiral and achiral molecules

Problem 4: diastereomers The Origin of optical Activity (GO AND READ)

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