ORGANIC - KLEIN 2E

CH. 18 - AROMATIC COMPOUNDS

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

CONCEPT: AROMATICTY INTRODUCTION

Aromatic compounds display an unusual stability for their high level of electron density.
Their high level of unsaturation should make them extremely reactive, however they are difficult to react with.

EXAMPLE: Three typical addition reactions with cyclohexene vs. benzene

What is responsible for this crazy level of stability? ___________________________

Categories of Aromatics:

_______________________________: These compounds possess an unusually ________ level of stability

_______________________________: These compounds do not possess any unique level of stability or instability

_______________________________: These compounds possess an unusually _____ level of stability. Very reactive!

EXAMPLE: Differing aromaticity of conjugated trienes

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS
CONCEPT: BENZENE NOMENCLATURE
Benzene was one of the first organic molecules to be identified (1825), so common names predominate.
Common Benzene Derivatives:
___________
__________________
_______________
Monosubstituted Benzene:
No location necessary
__________________ _________________
___________________ _________________
_________________________ _________________
Disubstituted Benzene: Multisubstituted Benzene:
No numerical locations Numerical locations necessary
1,2 = __________ (o-) Do not use -o, -m, -p
1,3 = __________ (m-)
1,4 = __________ (p-)
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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

EXAMPLE: Correctly name the following benzene derivatives.

1.

2.

3.

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

CONCEPT: FOUR TESTS OF AROMATICTY

For a compound to qualify as aromatic, it must meet 4 distinct tests. These are called Huckels Rule compounds.

1. Cyclic:

2. Fully Conjugated:

3. Planar:

4. Huckels Rule: (4n + 2) number of electrons

Any compound that _________ one or more of these tests is considered ____________________________

Any compound that meets all these conditions, but only has (4n) electrons is __________________________

These compounds are said to follow Breslows Rule

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

CONCEPT: COUNTING PI ELECTRONS

When counting -electrons, we are trying to identify the number of electrons that are freely available to circulate through
conjugated p-orbitals.

Double Bond/Anion = ________

Radical = ________

Cation = ________

EXAMPLE: Count the number of -electrons present in all of these molecules:

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

CONCEPT: AROMATICITY OF HYDROCARBONS

We can use our knowledge of the Four Tests of Aromaticity to confirm aromaticity

Huckels Rule = Aromatic (4n + 2) electron numbers: ______, _______, _______, _______, etc.
Breslows Rule = Anti-aromatic (4n) electron numbers: ______, _______, _______, _______, etc.
Non-aromatic = FAILS one or more test (including odd number of electrons)

EXAMPLE: Determine the aromaticity of the following molecules

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

CONCEPT: AROMATICTY OF ANNULENES

An annulene, sometimes referred to as a polyolefin, is the name given to a fully conjugated monocyclic hydrocarbon.

Due to their simple structure, rings of different sizes can be named as [n]annulenes, where n = number of carbons

As annulenes get bigger, the challenge becomes predicting planarity.

Predicting Annulene Planarity:

Pertaining to All-cis annulenes, EXAMPLE: Cyclooctatetrene vs. Cyclooctatetraene dianion

If 4n + 2 electrons
10+ = Non-aromatic
9 or less = Aromatic
If 4n electrons
8+ = Non-aromatic
7 or less = Antiaromatic

EXAMPLE: Determine if the following annulenes display any form of aromaticity.

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

CONCEPT: AROMATICITY OF HETEROCYCLES

Heterocycles are cyclic structures that contain a ______________________ within the ring.

Heteroatoms can choose to donate up to one lone pair each only if:

1. They are already sp3 hybridized

2. It will help to create aromaticity

EXAMPLE: Determine the aromaticity of the following heterocycles. Will any lone pairs be donated to the ring?

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

CONCEPT: INSCRIBED POLYGON METHOD

Also known as the polygon-in-circle method, or Frost Circle, this helps us visualize the identities of electrons and
molecular orbitals in a ring.

EXAMPLE: Use the polygon-in-circle method to predict stability of the following molecules.

Step 1: Draw polygon with one corner facing down.

Step 2: Draw molecular orbitals on all corners of ring
Step 3: Draw a line that splits the polygon down the middle
Step 4: Insert electrons into orbitals starting from lowest energy and working up (Aufbau Principle).

Filled molecular orbitals contribute to unique stability (aromaticity)

Partially filled molecular orbitals contribute to unique instability (antiaromaticity)

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

PRACTICE: Apply the polygon circle method to the following compound. Does it show any special stability? If yes, why?

Tropyllium cation

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

CONCEPT: ACIDITY OF AROMATIC HYDROCARBONS

Aromatic hydrocarbons are not naturally acidic. In fact, the pKa of benzene is ______

If a hydrocarbon can become aromatic by donating a proton, it will be uniquely acidic. i.e. cyclopentadiene

If a hydrocarbon becomes anitaromatic by donating a proton, it will be uniquely non-acidic. i.e. cycloheptatriene

EXAMPLE: Would the following hydrocarbon be expected to display unusual acidity? Explain your reasoning.

EXAMPLE: Would the following two hydrocarbons be expected to have similar acidities? Explain your reasoning.

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

CONCEPT: BASICITY OF AROMATIC HETEROCYCLES

Heterocycles often have multiple lone pairs available to react with acids. The question is which lone pair do we react?

EXAMPLE: Draw the product of the following acid/base reaction with imidazole.

Acids can only react with lone pairs that are not necessary for aromaticity.

sp2-hybridized lone pairs are basic.

EXAMPLE: Draw the product of the following acid/base reaction.

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

CONCEPT: SIDE-CHAIN HALOGENATION

The alkyl group directly attached to benzene is known as an alkyl side-chain.

The benzylic position of a side-chain is one of the most stable locations for radicals due to conjugation.

Recall that benzylic radicals are some of the most stable radical intermediates possible

Benzylic Resonance Structures:

Specific Side-Chain Halogenations:

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

CONCEPT: SIDE-CHAIN OXIDATION

The alkyl group directly attached to benzene is known as an alkyl side-chain.

Regardless of the length of an alkylbenzene side-chain, it can be oxidized to benzoic acid using hot KMnO4.

However, there must be at least one benzylic hydrogen present for oxidation to occur.

EXAMPLE: Which of the following alkylbenzenes would not yield benzoic acid when treated with hot KMnO4?

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

CONCEPT: BIRCH REDUCTION

The birch reduction is a dissolving metal reduction, except reacting with benzenes instead of alkynes.
The product of an unsubstituted benzene is a simple isolated cyclohexadiene.

Mechanism:

Regiochemistry:

Substituents affect the course of the mechanism, yielding regiospecific products.

______________________ groups isolate themselves from the diene

______________________ groups attach themselves to the diene

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

PRACTICE: Predict the major product from the Birch Reduction

CF3
2 Eq. Na, 2 Eq. t-buOH

Liq. NH3

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ORGANIC - KLEIN 2E
CH. 18 - AROMATIC COMPOUNDS

PRACTICE: Predict the major product from the Birch Reduction

CH3
2 Eq. Na, 2 Eq. t-buOH

Liq. NH3

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