SLE214 tutorial 4 (solutions)

Q1. Draw ALL resonance structures (using curly arrows) for the following species:

OH

O H

O H

O H

N O

N O

N O

OH

O H

very important res structure as all atoms have octet

Note: you can double the number of res structures for phenol by drawing the res form for benzene then repeating the process shown above. Also the nitro group has a resonance structure of its own.

Q2. Are the following aromatic, or could they possibly show some extra aromatic like stability due to polarity? Why/Why not? explain your answer Checklist for aromaticity: 1. cyclic 2. planar 3. Conjugated p orbitals (atoms must be sp2 or sp hybridised) 4. 2,6,10.....4n+2 es in the conjugated system

Satisfies all the rules, the carbocation is sp2 hybridised (as all ccats are) and so the molecule is aromatic. Unusually stable given its electron deficient, strained appearance.

H N1 N2

satisfies all the rules as N1 is sp2 hybridised with its lone pair included in the 4n+2 system (like pyrrole). N2 is sp2 hybridised with the lone pair out of the 4n+2 system (like pyridine).
O

doesnt satisfy requirements - especially as the carbonyl C is + means this is more like the cyclopentadienyl cation so is not very happy at all. A bit less stable than you might expect.
O

doesnt satisfy requirements but this time the + of the carbonyl means this is more like the tropanone cation which means its a little extra stable. Ideally you would have a fully e deficient C on the carbonyl C (to get 4n+2) but as that is impossible the + is not bad. Overall partial aromatic character. A bit more stable than you might expect.
H N

satisfies all requirements, the es that are bonded to the H are not part of the aromatic system (and werent to start with) so they have no effect on aromaticity if they bond with something else. Q3. Evaluate each of the following groups as either activating or deactivating when attached to a benzene ring? By what means are they activating or deactivating? Can you predict their directing effect?
O

+
O

Induction: weak Activiating Induction: Deactiviating Induction: Deactiviating Induction: dectiviating Resonance: not possible Resonance: Deactivating Resonance: Deactivating Resonance: activating the resonance effects dominate in this instance so this is an activating group overall

Q4. Draw the possible products ortho, meta, para (and their intermediate resonance structures) of the following electrophilic aromatic substitution reactions. Which product(s) ortho, meta, para is favoured and why?
N
Br2, FeBr3
ortho

N Br

N Br

N Br

N Br

N Br

N
meta

Br N
para

Br N Br N

Br N Br

Br

Br

Br

Br

Br

Br

N Br

4 res structs for the o and p intermediates make these more stable intemediates and hence the favoured reaction pathway.
O
O

N O

SO3, H+

Br

Cl AlCl3

Same treatment for these two gives meta product favoured for the sulfonation of the nitrobenzene and o,p products favoured for the bromobenzene