Isomerism

3.1 Isomerism in organic compounds

They have the same molecular formula but different arrangement of atoms.

3.2 Constitutional isomerism

Also known as structural isomerism. They are different compounds having the same molecular formula but different in their structure or connectivity. 3 types of constitutional isomerism: Chain isomerism, positional isomerism and functional group isomerism.

3.3.3 Chain isomerism

They have same number of carbon atoms. This isomerism arises due to possibility of branching in the carbon chain. They have the same functional group same chemical properties. Due to difference in carbon backbones, they have different physical properties.

Note: The chemical properties of every organic molecule, regardless of size and complexity, are determined by the functional group.

Example 1:
Categorize this pair of structures.

On first look, it seems that these molecules have different carbon backbone arrangement. However, for molecules to be isomers, they must have the SAME molecular formula. These molecules DO NOT have the same chemical formula (C6H14 and C6H12).

So, they are NOT isomers.

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Example 2: Categorize this pair of structures.

These structures have the same chemical formula of C6H14. They do not have the same sequence of carbon backbone connections. The methyl group on the third carbon versus the methyl group on the second carbon. So, they are chain isomers (constitutional isomers).

Example 3: Draw all possible isomers of C7H16.

Always start with the simplest structure. Ensure that there are no repeated structures. For example:

Do a 1800 flip for either one of the structures, you will get the other. These two structures are identical.

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3.3.4 Positional isomerism
Example 4: Categorize this pair of structures. They have the same carbon backbone arrangement. They must have the same functional group. Only position of the functional group differs. Same chemical properties and different physical properties.

These structures have the same molecular formula. They look almost identical except for the position of the double bond. Double bond is on the second carbon versus double bond on the third carbon.

Therefore, they are positional isomers (constitutional isomers). Example 5: Draw all possible positional isomers of bromophenol.

Always start with the simplest structure. Take note of repeated structures

These two structures are identical. 3

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3.3.5 Functional group isomerism
Same molecular formula with different functional group.

Example 6:

Both have the same molecular formula of C5H10O2. However one is an ester and the other is a carboxylic acid. Note: There is actually no need to draw out the structures. As long as they have same molecular formula and have different functional group, they are functional group isomers. Other examples: Propanal (aldehyde), CH3CH2CHO and propanone (ketone), CH3COCH3 Ethanol (alcohol), CH3CH2OH and methoxymethane (ether), CH3OCH3

3.3 Stereoisomerism
They have the same molecular and structural formulae but the atoms in the molecules have different spatial arrangement. 2 types of stereoisomerism: Geometric isomerism and optical isomerism.

Note: Different spatial arrangement means the atoms or groups of atoms in the molecules are directed differently in 3-dimensional space.

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3.3.1 Geometric isomerism
This isomerism arises due to restriction to free rotation of certain parts of the molecule due to multiple bonds or ring structure. Geometric isomers exist in pairs and they have different physical properties.

Example 7:

Cis-isomer has two methyl groups on the same side of the double bond. Trans-isomer has the methyl groups on opposite sides. Note: Cis-trans naming system only works with disubstituted alkenes. Trisubstituted and tetrasubstituted double bonds follow a E,Z system. Example 8:

Cis-isomer has two groups on the same side of the double bond. Trans-isomer has the two groups on different sides of the double bond.

Note: Compounds that have one of their carbons bonded to identical groups CANNOT exist as cistrans isomers.
Examples:

Geometric isomerism cannot occur because either carbon in each compound has two identical groups 5

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3.3.2 Optical isomerism
There are two classifications under optical isomerism: Diastereomers and Enantiomers.

Enantiomers
A structure without a plane of symmetry and not superimposable on its mirror image is a chiral molecule and can exist as two enantiomers. In order for a molecule to be chiral; - Contains stereogenic centre, that is, a carbon atom attached to four different atoms or groups of atoms. - It does not have a plane of symmetry. - Not superimposable on its mirror image.

Note: Chiral molecule chiral centre Stereogenic centre/chiral centre/stereocentre/asymmetric carbon atom/asymmetric carbon centre = A carbon atom attached to four different atoms or groups of atoms. Chiral molecule = molecule that have no plane of symmetry

H2N R

OH H

And so the other enantiomer( mirror image) is

H2N R H OH

This structure fufills all the criterias as a chiral molecule.

To go from one enantiomer to another (its mirror image), all stereogenic centres are inverted. Inverted here means from into the plane to out of the plane and vice versa.

Example 9: Categorize this pair of structures.

They have the same chemical formula (C6H14O2). they are isomers. They have the same sequence of carbon backbone. they are not constitutional isomers. By comparing the two structures, both stereogenic centres are inverted there are mirror images of each other they are enantiomers. 6

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Example 10: Categorize this pair of structures.

They have the same molecular formula of C13H10N2O4. they are isomers. They have the same sequence of carbon backbone. they are not constitutional isomers. Compounds cannot be interconverted by rotation about single bonds. they are not conformational isomers. After concluding they are stereoisomer, here are the general steps to see if they are enantiomers. 1. Rotate about single bond for either one of the structure (A) so that the positions of atoms are the same for both structures.

2. Now compare structure B and C, the stereogenic centre is inverted. they are enantiomers. Note: When doing an 1800 rotation, bonds on the plane remain on the plane. Bonds out of the plane go into the plane after rotation and vice versa. Enantiomers have identical physical and chemical properties. Enantiomers can be distinguished from each other by their ability to rotate a plane of polarised light in the opposite directions by the same extent. When equal proportions of enantiomers are mixed together, the rotating property of one excatly cancel out the other. Such mixture of two enantiomers in equal proportions is called racemic mixture.

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Diastereoisomer
Diastereaisomers are stereoisomers that are not enantiomers. They are stereoisomers that are not mirror images. Diastereoisomers can be chiral or achiral. To go from one diastereoisomer to another, only one of the stereogenic centres is inverted.

Note: Achiral structure is structure with plain of symmetry. Example 11:

Categorize this pair of structures

They have the same molecular formula. they are isomers. They have the same sequence of carbon backbone. they are not constitutional isomers. Compounds cannot be interconverted by rotation about single bonds. they are not conformational isomers. Atoms are in the same position but only one of the stereogenic centres is inverted they are diastereoisomers. They have different physical and chemical properties.

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Note: Quick flow chart for classification of isomers