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Lecture 33 PDF

This document summarizes key points from a lecture on stereochemistry: 1) Enantiomers behave differently in a chiral medium and are named using Cahn-Ingold-Prelog rules. Optical rotation and R/S designation are independent. 2) Chiral compounds rotate the plane of polarized light while achiral compounds do not. Specific rotation is a standardized measurement of optical activity. 3) Enantiomeric excess describes the ratio of one enantiomer to the other in a mixture. Meso compounds contain stereocenters but are achiral due to symmetry. 4) Molecules with multiple stereocenters can have diastereomers that differ in

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76 views18 pages

Lecture 33 PDF

This document summarizes key points from a lecture on stereochemistry: 1) Enantiomers behave differently in a chiral medium and are named using Cahn-Ingold-Prelog rules. Optical rotation and R/S designation are independent. 2) Chiral compounds rotate the plane of polarized light while achiral compounds do not. Specific rotation is a standardized measurement of optical activity. 3) Enantiomeric excess describes the ratio of one enantiomer to the other in a mixture. Meso compounds contain stereocenters but are achiral due to symmetry. 4) Molecules with multiple stereocenters can have diastereomers that differ in

Uploaded by

Rachit Shah
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry


II-Semester: AY 2018-19
Lecture 33 (08-04-2019)
BITS Pilani, Pilani Campus
Summary of Lecture 32

Enantiomers behaves differently in chiral medium


How do we “name” an enantiomers?? Cahn-Ingold-Prelog rules: THE R/S SYSTEM

The sign of optical rotation is not


related to the R,S designation. Either of
them can be dextrorotatory or
levorotatory.
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Physical Properties of Stereoisomers—Optical Activity

• The chemical and physical properties of two enantiomers


are identical except in their interaction with chiral
substances. They have identical physical properties, except
for how they interact with plane-polarized light.

• Plane-polarized (polarized) light is light that has an electric


vector that oscillates in a single plane. Plane-polarized light
arises from passing ordinary light through a polarizer -Polaroid
filter. The resulting light is said to be polarized - all its vibrations
are parallel to a single plane.
• A polarimeter is an instrument that allows polarized light to
travel through a sample tube containing an organic compound.
It permits the measurement of the degree to which an organic
compound rotates plane-polarized light.
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Plane-Polarized Light and Polarimeter

 With achiral compounds, the light that exits the sample tube
remains unchanged. A compound that does not change the
plane of polarized light is said to be optically inactive.

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Plane-Polarized Light and Polarimeter

 With chiral compounds, the plane of the polarized light is rotated


through an angle . The angle  is measured in degrees (°), and is
called the observed rotation. A compound that rotates polarized light
is said to be optically active.

The angle of rotation of plane polarized light by an optically active


substance is proportional to the number of atoms in the path of the light.
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Specific Rotation
Specific rotation is a standardized physical constant for the
amount that a chiral compound rotates plane-polarized light.
Specific rotation is denoted by the symbol [] and defined using a
specific sample tube length (l, in dm), concentration (c in g/mL),
temperature (25 oC) and wavelength (589 nm).
(observed rotation in degrees) 
[l ]D  
(pathlengt h in dm)(concen tration in g/ml) l  C
Where [α]D = Specific rotation, α = observed rotation, C = concentration in g/mL, l =
length of tube in dm.
Q: A compound was isolated in the lab and the observed roation was
+15 when measured in a 1 dm. tube containing 2.0 g of sample in 10 mL
of water. What is the specific rotation of this compound?
[]D = /(length x (g/ml)) = 15/(1 dm. X (2.0 g/10 ml)) = +75o
Dextrorotary designated as d or (+), clockwise rotation
Levorotary designated as l or (-), counter-clockwise rotation
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Optical Purity and enantiomeric excess (ee)
A quick word on enantiomeric excess (ee)
Enantiomeric excess (ee) is the most common way to report the level of
enantioselectivity Observed for a reaction.
The ee is the amount (in %) of one enantiomer present subtracted
from the amount of the other, thus…..
50:50 0% ee
75:25 50% ee
80:20 60% ee Q: What is the ee of the racemic
mixture with 95% A and 5% B?
90:10 80% ee
95:5 90% ee ee = % of A - % of B = 95 – 5 = 90%
99:1 98% ee
99.0:0.5 99% ee
If the mixture contain one of the enantiomerin excess to other, the
mixture will show optical activity. If a subtancecontain exclussivelyone
enantiomers, the substance is called optically pure substance
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Optical Purity and enantiomeric excess (ee)
Enantiomeric excess (optical purity) is a measurement of how
much one enantiomer is present in excess of the racemic mixture.
It is denoted by the symbol ee.

Q: The observed rotation for an enantiomeric mixture of limonene is +109o. Calculate


the (%) of each enantiomer present in the solution. (Rotation of pure enantiomer +123o).

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Molecular Symmetry

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Molecular Symmetry and Chirality

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Multiple Stereocenters
3-Chloro-4-methylhexane There are two chiral centers

They have diastereomeric relationship. Stereoisomers that are not


enantiomers (non-superimosable mirror images) are called
diastereoisomers.
Diastereoisomers have different physical and chemical property.
For n chiral centers = 2n maximum stereoisomers
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Multiple Stereocenters

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Multiple Stereocenters
3,4-Dichlorohexane

(3R, 4R)

A meso-compound is one which is superimposable on its mirror image even


though it contains stereogenic centers. The molecule is achiral.

Compounds contains
stereogenic center but achiral
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Multiple Stereocenters: Meso compounds

Meso compound Plane of symmetry Superimposable


Optically inactive

Internal plane of symmetry


Point of inversion or
Internal plane of symmetry
center of symmetry
Optically inactive
Optically inactive
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Disubstituted cyclic molecules
 Consider 1,3-dibromocyclopentane. Since it has two stereogenic
centers, it has a maximum of four stereoisomers.

 A disubstituted cycloalkane can have two substituents on the same


side of the ring (cis isomer, A) or on opposite sides of the ring (trans
isomer, B). These compounds are stereoisomers but not mirror
images.

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Disubstituted cyclic molecules

The cis isomer is superimposable on its mirror image, making the images
identical. Thus, A is an achiral meso compound.

The trans isomer is not superimposable on its mirror image, labeled C,


making B and C different compounds. Thus, B and C are enantiomers.
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Disubstituted cyclic molecules
Non-superimposable mirror image
Rotate

Conformational isomers

Two can not be separated, optically inactive.

Rotate
Optically active

Same molecule
 If the contributing conformations average out to an achiral conformation,
then the molecule is considered achiral and If a chiral conformation
prevails over the others, then the molecule is considered chiral and it will
show optical activity.
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Geometrical isomerism

Cahn-Ingold-Prelog convention
• If the higher priority groups are on the same side
the stereoisomer is called as ‘Z’.
• If the higher priority groups are on the opposite side
the stereoisomer is called as ‘E’.
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