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PM 1
Experimental aromatic resonance energy
Adding another double bond and forming a cyclic system is worth about 29
kcal/mol = aromatic resonance energy
PM 2
Not all rings are created equal
+56 kcal
28 kcal
Frost circles are a mnemonic for identifying MOs of mono-cyclic aromatic systems.
PM 4
Cyclopropenyl system
Cyclopropenyl cations are so stable (A-res-E +25 kcal/mol) that some could be kept in a
bottle, and with some substituents (like 1,2,3-tri-t-butylcyclpropenyl cation) they may be
crystallized from water (i.e. the carbocation is more stable than the alcohol).
Cyclopropenyl anion is so unstable (A-res-E 21 kcal/mol) that it has never been directly
observed (despite numerous attempts).
The cyclopentadienyl anion is aromatic. The stability (A-res-E +20 kcal/mol) of the anion is
reflected in the pKa of the hydrocarbon. Cyclopentadiene is as acidic as water (pKa= 16).
PM 7
Cycloheptatrienyl system
The cation is aromatic, stable and its salts can be kept in a bottle. It forms easily
when cycloheptatriene reacts with Br2.
The anion is antiaromatic, it can only be observed at low temperature and it is very reactive.
PM 8
Applications of substitution: ethers
The rule strictly applies to mono-cyclic systems, but if applied carefully, it also
covers polycyclic systems.
1. aromatic (extra stabilized): molecules with planar (or nearly planar), cyclic systems
with (4n+2) electrons
2. antiaromatic (extra destabilized): molecules with planar (or nearly planar), cyclic
systems with (4n) electrons
3. non-aromatic: neither of the above category
PM 10
Aromatic heterocycles
Ar-res-E (kcal/mol)
(benzene 36 kcal/mol)
PM 11
Larger rings and polycyclic aromatics
If criteria for aromaticity are met. Many unusual structures can exhibit aromatic stabilization.
PM 12
Aromaticity and structure
PM 14
Aromatic electrophilic substitutions
PM 15
Substitution vs. addition
1. 1st step is rate limiting: destruction of aromatic stabilization even if the carbocation
is resonance stabilized).
2. Usually, E+ has to be more reactive (positively charged; i.e. more electron deficient)
than in electrophilic additions to alkenes.
3. A proton removal in the second step by X re-establishes aromatic stabilization (no
addition is observed). (E1 is faster than SN1)
PM 16
Preparing strong electrophiles
Strong electrophiles are prepared with the help of Lewis or Brnsted acids.
PM 17
Substitution: examples
PM 18
Nitration of toluene
For chlorine (and halogens in general) inductive effects dominate resonance effects.
PM 22
Substituent effect
EWG EDG
PM 23
Substituent effect
(one H in benzene = 1)
Z any atom with a lone pair V and W are any atoms as long
as W is more electronegative than V
o-, p- directing (C=O, N=O, S=O, C=N, CN)
PM 24
Substituent effect: multiple substituents
sterics
directing effects directing effects in
in agreement disagreement;
EDG will dominate
directing effects
directing effects in disagreement;
In agreement; stronger EDG will
strong activation dominate
PM 26
Aromatic ring hydrogenation
Diastereoselectivity is variable
Any reducible side group are also reduced (C=C, CC, C=O, NO2)
PM 27
Substituent reduction
Directly bonded (aromatic) nitro groups (-NO2) and carbonyl groups (-C=O) are easily
reduced (by hydrogenation or otherwise).
PM 28
Problems with Friedel-Crafts reactions
+ + +
The products are more reactive than the starting material => multiple alkylations
PM Further complications: carbocation rearrangements 29
Friedel-Crafts acylation
Friedel-Crafts acylation solve the over alkylation problem. The ketone is an EWG
group so no further acylation takes place.
The aromatic ketone can be reduced to methylene group (=> product of alkylations).
PM 30
Phenol synthesis
Oxygen electrophiles for aromatic substitution are not know; indirect methods is used.
PM 31
Aromatic synthesis: substituents
PM 33