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Week5&6 OrgChem1 Stereochemistry Part2 2014

It is explains the Avogadro number the moles and mole radios Even molecular formulas

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Lillian Kakole

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0% found this document useful (0 votes)

26 views

Week5&6 OrgChem1 Stereochemistry Part2 2014

It is explains the Avogadro number the moles and mole radios Even molecular formulas

Uploaded by

Lillian Kakole

We take content rights seriously. If you suspect this is your content, claim it here.

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Week 5 & 6 – Part 2

Stereochemistry :
The Arrangement of
Atoms in Space

Compiled by C. RAIDRON

© 2014 Pearson Education, Inc.

Plane-Polarized Light
• Enantiomers have the same physical properties
e.g. bp’s, mp’s, solubilities.
• Enantiomers do not interact the same with plane-polarized
light.

© 2014 Pearson Education, Inc.

An Achiral Compound is Optically Inactive

An achiral compound does not rotate

the plane of polarization of plane-polarized light.

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A Chiral Compound is Optically Active

A chiral compound rotates

the plane of polarization of plane-polarized light.
If it rotates the plane clockwise) = (+) and said
to be dextrorotatory.
If it rotates the place counterclockwise = (–) and
said to be levorotatory.
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R and S Versus (+) and (–)

Some R enantiomers are (+) and some are (–).

Some S enantiomers are (+) and some are (–).

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A Polarimeter

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The Polarimeter
 A device for measuring the optical activity of
a chiral compound
 = observed
optical rotation

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Specific Rotation
observed
temperature rotation
25 
[]D =
c x ℓ
wavelength
concentration length of cell
of light
of sample in dm
(e.g. D-line of
solution (1 dm = 10 cm)
Na lamp,
in g/mL
=589.6 nm)
© 2014 by John Wiley & Sons, Inc. All rights reserved.
© 2014 Pearson Education, Inc.
If One Enantiomer Is (+),
the Other Is (–)

The mirror-image molecule rotates the plane

of polarization the same amount but in
the opposite direction.
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Two enantiomers should have the
same value of specific rotation, but the
signs are opposite
e.g. 2-butanol
CH3 CH3
* *
H CH2CH3 H3CH2C H
HO OH

25 o 25 o
[] = + 13.5 [] =  13.5
D mirror D

© 2014 by John Wiley & Sons, Inc. All rights reserved.

© 2014 Pearson Education, Inc.

If One Enantiomer Is (+),
the Other Is (–)

• A mixture of equal amounts of two

enantiomers is called a racemic mixture or a
racemate.
• Are optically inactive.
• (±) is used to specify a racemic mixture.
© 2014 Pearson Education, Inc.
Racemic Forms and Enantiomeric
Excess
 A sample of an optically active
substance that consists of a single
enantiomer is said to be
enantiomerically pure or to have an
enantiomeric excess of 100%

© 2014 by John Wiley & Sons, Inc. All rights reserved.

© 2014 Pearson Education, Inc.

Enantiomeric Excess
Enantiomeric excess tells us how much of an
excess of one enantiomer is in a mixture.

e.g. 2-bromobutane: observed specific rotation of +9.21,

• i.e. 40% of the mixture is excess S enantiomer and

60% is a racemic mixture.
• 70% of mixture is the S enantiomer and 30% is the
R enantiomer.
© 2014 Pearson Education, Inc.
 Enantiomeric excess (ee)
● Also known as the optical purity

● Can be calculated from optical

rotations
% enantiomeric observed specific rotation
= x 100
excess * specific rotation of the
pure enantiomers
© 2014 by John Wiley & Sons, Inc. All rights reserved.
© 2014 Pearson Education, Inc.
5.7 Identify the type isomer for
(R)-2-pentanol.

a) Dextrorotatory isomer
b) Levorotatory isomer
c) Has to be experimentally determined
d) Neither

© 2014 Pearson Education, Inc.

5.7 Identify the type isomer for (R)-2-pentanol.

a) Dextrorotatory isomer
b) Levorotatory isomer
c) Has to be experimentally determined
d) Neither

Explanation:
Dextrorotatory and levorotatory isomers
must be experimentally determined.
What’s the name of the instrument?
© 2014 Pearson Education, Inc.
5.8 Calculate specific rotation of 5.00 g/20.0 mL;
observed rotation of -40°; 5 dm cell.

a) -32°
b) 32°
c) 2°
d) -2°

© 2014 Pearson Education, Inc.

5.8 Calculate specific rotation of 5.00 g/20.0 mL;
observed rotation of -40°; 5 dm cell.
a) -32°
b) 32°
c) 2°
d) -2°

Explanation:
[α] = (-40)/[(5/20)(5)]

© 2014 Pearson Education, Inc.

5.9 Explain an enantiomeric excess of 30% (-).

a) 70% (+) and 30% (-)

b) 70% (-) and 30% (+)
c) 65% (+) and 35% (-)
d) 65% (-) and 35% (+)

© 2014 Pearson Education, Inc.

5.9 Explain an enantiomeric excess of 30% (-).

a) 70% (+) and 30% (-)

b) 70% (-) and 30% (+)
c) 65% (+) and 35% (-)
d) 65% (-) and 35% (+)

Explanation:
The 30% (-) enantiomeric excess is the
difference between (+) and (-).
© 2014 Pearson Education, Inc.
Diastereomers

1 and 2 are enantiomers. 3 and 4 are enantiomers.

Diastereomers are stereoisomers that are not
enantiomers.
1 and 3 are diastereomers. 2 and 3 are diastereomers.
1 and 4 are diastereomers. 2 and 4 are diastereomers.
Diastereomers have different physical and chemical properties.
© 2014 Pearson Education, Inc.
Enantiomers & Diastereomers
 Stereoisomers can be subdivided into two
general categories:
enantiomers & diasteromers
● Enantiomers – stereoisomers whose
molecules are nonsuperimposable
mirror images of each other
● Diastereomers – stereoisomers whose
molecules are not mirror images of each
other

© 2014 Pearson Education, Inc. © 2014 by John Wiley & Sons, Inc. All rights reserved.
 Geometrical isomers
(cis & trans isomers) are:
● Diastereomers
e.g.
Ph
Ph Ph and Ph
(cis) (trans)

Cl Cl Cl H
and
H H H Cl
(cis) (trans)
© 2014 by John Wiley & Sons, Inc. All rights reserved.
© 2014 Pearson Education, Inc.
Subdivision of Isomers
Isomers
(different compounds with same
molecular formula)

Constitutional Isomers Stereoisomers

(isomers whose atoms (isomers that have the same
have a different connectivity but differ in spatial
connectivity) arrangement of their atoms)

Enantiomers Diastereomers
(stereoisomers that are (stereoisomers that are
nonsuperimposable mirror NOT mirror images of
images of each other) each other)

© 2014 Pearson Education, Inc.

maximum # of stereoisomers = 2n
(n = # of asymmetric centers)

1 and 2 are enantiomers. 3 and 4 are enantiomers.

© 2014 Pearson Education, Inc.

Perspective Formulas of the Four
Stereoisomers

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Perspective Formulas of the Four
Stereoisomers

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Perspective Formulas of the Four
Stereoisomers

Erythro enantiomers: with hydrogens on same side

of carbon chain
Threo enantiomers: with hydrogens on the opposite
sides
© 2014 Pearson Education, Inc.
How to Draw Stereoisomers for
Molecules Having More than One
Chirality Center

© 2014 by John Wiley & Sons, Inc. All rights reserved.

© 2014 Pearson Education, Inc.

 Start by drawing the portion of the
carbon skeleton that contains the
chirality centers in such a way that as
many of the chirality centers are placed
in the plane of the paper as possible,
and as symmetrically as possible

© 2014 by John Wiley & Sons, Inc. All rights reserved.

© 2014 Pearson Education, Inc.

 Next we add the remaining groups that
are bonded at the chirality centers in
such a way as to maximize the
symmetry between the chirality centers

© 2014 by John Wiley & Sons, Inc. All rights reserved.

© 2014 Pearson Education, Inc.

 To draw another stereoisomer, we
interchange two groups at any one of
the chirality centers
• All of the possible stereoisomers for a
compound can be drawn by successively
interchanging two groups at each chirality
center

© 2014 Pearson Education, Inc. © 2014 by John Wiley & Sons, Inc. All rights reserved.
 Next we examine the relationship
between all of the possible pairings of
formulas to determine which are pairs
of enantiomers, which are
diastereomers

© 2014 by John Wiley & Sons, Inc. All rights reserved.

© 2014 Pearson Education, Inc.

 Structures 1 and 2 are enantiomers; structures
3 and 4 are also enantiomers
 Structures 1 and 3 are stereoisomers and they
are not mirror images of each other. They are
diastereomers
• Diastereomers have different physical
properties - different melting points and
boiling points, different solubilities, and so
forth © 2014 by John Wiley & Sons, Inc. All rights reserved.
© 2014 Pearson Education, Inc.
Meso Compounds
• A meso compound contains at least two
stereogenic centers, yet the molecule itself is
achiral. This is because meso compounds contain
an internal plane of symmetry.

 each half is a mirror image of the other

Plane of symmetry (= mirror plane)  an imaginary plane that bisects a
molecule in such a way that the two halves of the molecule are mirror images
of each other. Plane may pass through atoms, between atoms or both. 37
© 2014 Pearson Education, Inc.
Two Asymmetric Centers: Three Stereoisomers
(a meso compound and a pair of enantiomers)

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A Meso Compound Has a
Superimposable Mirror Image

A meso compound is:

• optically inactive even though it has asymmetric
centers.
• Achiral, because it is superimposable on its mirror
image.
© 2014 Pearson Education, Inc.
A Meso Compound Has a
Plane of Symmetry

They are easy to recognise, because the four atoms or

groups bonded to one asymmetric centre are identical
to the four atoms or groups to the other asymmetric
centre.

© 2014 Pearson Education, Inc.

A Meso Compound

A compound with two asymmetric centers that have

the same four groups bonded to each asymmetric
center will have three stereoisomers:
a meso compound and a pair of enantiomers.
© 2014 Pearson Education, Inc.
Naming Stereoisomers

© 2014 Pearson Education, Inc.

Naming Stereoisomers

© 2014 Pearson Education, Inc.

Naming Stereoisomers

© 2014 Pearson Education, Inc.

Physical Properties of Stereoisomers

Separating Enantiomers:
Resolution of a racemic mixture

separating by hand

Physiological Properties of Enantiomers