EXPERIMENT 6

INTRODUCTION TO STEREOCHEMISTRY

I. Introduction

Stereochemistry is concerned with the shapes of molecules and how the differences in shapes can
affect the properties and reactions of compounds. Subtle differences in molecular shape have far-reaching
consequences and it is probably the field of molecular biology that a full awareness of molecular shapes
has emerged. Knowledge of the molecular shapes of vital compounds such as sugars, amino acids, and
proteins is essential in understanding their reactions and properties.

Molecular structures are so frequently represented in two dimensions that we often experience
considerable difficulty in thinking about molecules in three dimensions. The purpose of this exercise is to
persuade you to think in three dimensions.

II.Chirality, Enantiomerism, Diastereomerism and Optical Activity

Objects which are IDENTICAL are SUPERIMPOSABLE that is, when we imagine the two objects
are used together, all the corresponding parts match exactly. Thus, a sphere is superimposable on
another sphere of the same diameter. A sphere, however, is not superimposable on a cube nor on a sphere
of a different diameter.

1. Determine whether the following pairs of objects are superimposable or not superimposable with each other
a) two forks b) your left hand and your right hand

2. Yes or No. View your right hand in front of the mirror

a) Is the reflection of your right hand superimposable on your left hand?

b) Is your right hand the mirror image of your left hand?

3. Using a mirror, decide whether the following objects are superimposable or not superimposable on their
mirror images.

a) a fork b) a pentagon c) your left hand

A PLANE OF SYMMETRY is an imaginary plane or sheet that divides the objects so that one half is
exactly a reflection of the other half.

4. Yes or No. Tell whether the following objects contain at least one plane of symmetry.

a) a sphere b) a regular tetrahedron c) a shoe

5. Determine whether the objects in No. 4 are superimposable or not superimposable on their mirror images

6. Describe the relationship between the presence of a plane of symmetry in an object and the objects
superimposability on its mirror image in your own words.

Objects which are not superimposable on their mirror images are CHIRAL objects, while
those which are superimposable on their mirror images are ACHIRAL.

7. Look for the model of CH4. Is it chiral or achiral? Why?

1
8. Look for the model of CBrFClH. Is it chiral or achiral? Why?

Nonsuperimposable mirror images are called ENANTIOMERS.

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 9. a) Are enantiomers chiral?
b) Do enantiomers have the same molecular formula?
c) Does one structural formula represent both members of a pair of enantiomers?

10. Are enantiomers stereoisomers?

One of the most important property of chiral molecules is their effect on plane polarized light. Both
enantiomers rotate the plane of polarized light. Substances with this property are said to be optically
active. Chiral substances containing molecules which are not superimposable on their mirror images are
optically active. Enantiomers are also known as optical isomers.

11. Determine whether each of the following are optically active or optically inactive.

a) CH3CH(NH2)COOH
b) CH3CH2CHClCH3
c) CH3CH2CH2CH3

The rotation of the plane polarized light is used to observe experimentally one of the main
differences between a pair of enantiomers. One enantiomer rotates plane polarized light clockwise (as
seen by the observer), the other enantiomer, counterclockwise by the same amount. Conventions used to
indicate the direction of rotation of the plane of polarization are:

Clockwise (+): dextrorotatory, d

Counterclockwise ( - ): levorotatory, l
12. Which enantiomer of alanine rotates the plane polarized light clockwise?

13. Which of the following aqueous solutions are likely to be optically inactive?

a) a solution of ethanol, CH3CH2OH

b) a solution of (+) alanine
c) a solution of (-) alanine
d) a solution containing equimolar quantities of (+) alanine and (-) alanine

A mixture containing equimolar quantities of a pair of enantiomers is called a RACEMIC MIXTURE

14. How is the racemic mixture of alanine represented?

15. Examine the models for the presence of a plane of symmetry. Which of them has at least one plane of
symmetry?

(a) (b) (c) (d)

16. Which are superimposable on their mirror image?

17. Which model represents a chiral molecule?

18. How many different atoms or groups of atoms must be attached to the central carbon atom in order to
confer chirality to the molecule?
 Consider the following structural formula for Nos. 19-20

(a) (b)
19. Which is a chiral molecule?

20. Which can exist as a pair of enantiomers? Draw the pair of enantiomers.

Now we will consider molecules with more than one chiral center. Consider 2,3-dihydroxybutanoic
acid.

The flying wedge representation of 2,3-dihydroxybutanoic acid is shown below.

Mirror image

(I)

(II)
22. a) Draw the flying wedge representation of its mirror image (II)
b) Are I and II chiral?

A compound which contains two different chiral centers can exist as four optically active
stereoisomers. The flying wedge representation of the four stereoisomeric 2,3-dihydroxybutanoic acid are
given below.

Some are related as enantiomers while others, called DIASTEREOMERS are not related as mirror
images at all.

23. What is the relationship between?

 a) I and II b) III and IV c. I and IV d. II and IV

24. What is the relationship between?

a) I and III b) II and III

 CONFORMATIONS. Atoms within the molecules can vibrate and are free to rotate about the single
bond. This rotation may result in the atom taking different positions relative to the rest of the molecule.
Molecular structures that are interconvertible by simple bond rotations are called conformations.

OPEN CHAIN COMPOUNDS

25. Look for the model of ethane. Rotate the C C single bond.

a) Is there a change in the relative positions of the different atoms as the C-C bond is rotated?
b) Does the ethane molecule have more than one conformation?

Ethane can adopt an infinite number of conformations but the two extreme conformations are
eclipsed and staggered.
Newman Projection:

Eclipsed Staggered

Sawhorse Projection:

Eclipsed Staggered
26. In which extreme conformation are the hydrogens farthest apart from each other?

27. Draw the Newman and Sawhorse representation of ethane with the highest potential energy.

28. Draw the Newman and Sawhorse representation of ethane with the lowest potential energy.

29. Which is the preferred conformation of ethane?

30. Look at the model of chloroethane.

a) Do all chloroethane molecules spend all of their time in this preferred conformation?
b) What is the preferred conformation called?

RING COMPOUNDS

31. Look at the model of cyclohexane. Rotate the carbon atoms and examine the different conformations

a) Are there any conformation in which all carbon atoms of the ring are in one plane?

The two extreme conformations of cyclohexane are referred to as chair and boat :

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 Put your model carefully in the chair conformation. Look at the relative positions of the hydrogen
atoms along the axes C2 C3 and C5 C6. Hold carbons 2, 3, 5, and 6 firmly in one hand, then without
moving carbon 1, flip carbon 4 up (or down) without breaking any bond. Again look at the relative positions
of the hydrogens along the C2 C3 and C5 C6 bonds.

32. Does flipping of carbon 4 result in a change in conformation?

33. In which conformations are the hydrogens farthest apart?

34. Which is the preferred conformation?

Compare your models with the Newman Projections below by looking through the C2 C3 and C5
C6 bonds at the same time.

35. Which is the eclipsed conformation?

36. Which is the staggered conformation?

In the chair conformation, there are two conformations of the hydrogen atoms. Bonds that are
oriented vertically are called axials bonds while the rest known as equatorial bonds.

37. Mark the axial bonds. Hold carbon atoms 1, 2, 3, 4, 5, and 6 firmly and flip up carbon 4. What is the resulting
conformation?

38. Then holding carbons 2, 3, 4, 5, and 6 firmly, flip down carbon 1. What is now the resulting conformation?

39. Did you break any bonds?

40. What is the orientation of the marked bonds now?

41. Make a sketch of the final conformation showing the marked bonds.

Now with the equatorial bonds marked, reverse the process and rotate the bonds to reform the chair
conformation with the axial bonds marked. This overall process of one chair conformation changing to
another chair conformation is called RING INVERSION.

42. Represent the process using the symbol () to indicate that the two chair conformations are in
dynamic equilibrium.

43. Construct a model of methycyclohexane with the methyl attached axially. Make the ring undergo inversion
and complete the following:

(a)
 44. a) In which chair conformation (a or b) is the methyl
group farthest from the neighboring hydrogen atom?
b) In which chair conformation (a or b) does the
methyl group have greater room?
c) Which is the preferred conformation of
mthylcyclohexane (a or b)? (b)

45. Make a general statement about the preferred conformation of monosubstituted cyclohexanes.