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Benzene Chemistry part 2

A large part of this topic is knowing how to generate various electrophiles and then apply the basic
mechanism we went through in part 1.

Electrophiles required: NO2+, Cl+ or Br+, R+ (alkyl) and RC+=O (acyl)

NO2+ (nitro group)


You need to use a mixture of concentrated nitric acid and sulphuric acid. They often ask for the equation:

HNO3 + H2SO4 H2+NO3 + HSO4-

in this case and many others, sulphuric acid acts as a catalyst, which simply means it supplies an H +.

From the equation above, water is then lost and the electrophile is formed:

H2+NO3 NO2+ + H2O

The mechanism to then form nitrobenzene is identical to that in part 1.

Regenerating the catalyst


Questions often ask you to show that for example H 2SO4 is acting as a catalyst. There are two ways to do
this:

In the mechanism
Instead of just losing the H atom we can use the HSO4- formed initially to remove the H+ and reform the
H2SO4 catalyst.

In an equation

You can also write out an equation to show this.

HSO4- + H+ H2SO4

you can use either method. If they dont ask for it then you can just draw the mechanism as normal.

Polysubstitution

A problem associated with this nitration reaction is polysubstitution.

You must keep the temperature below 55 C to get the monosubstituted compound i.e. just one NO 2
group.

If the temperature is higher than 55 C you will get more than one NO2 group, such as:

Aminobenzene (NH2)

One reason that they make the nitro compound is so that they can make the amine (NH 2) from it. The NH2
compound cannot be made directly in benzene chemistry, as it would involve adding a nucleophile.
Benzene does not like nucleophiles and repulsion would occur.

NO2 NH2

This reaction is worth knowing as it comes up a lot in exams...it is reduction using tin and HCl. No
mechanism is required:
Friedel-Crafts Reactions
There are two parts to this: Friedel-Crafts alkylation and Friedel-Crafts acylation.

Alkylation
A typical alkylation product might look like this:

To identify the electrophile used, all that you need to do is break the bond between benzene and the alkyl
group and put a + sign on the alkyl part.

Remember that the electrophile is not the reagent but something that is generated in the reaction
mixture. To get the starting material, simply add a Cl to the electrophile to give, in this example, CH 3-CH2-
Cl.

the starting reagent that you need for alkylation is a haloalkane

Therefore the reagent we need to use is CH3CH2Cl.

To generate the electrophile from the starting reagent, the haloalkane is reacted with a Friedel-Crafts
catalyst. This is sometimes referred to as a halogen carrier. AlCl3 or alternatively FeBr3 are used (both do
the same thing).

The catalyst polarises the haloalkane, which results in the formation of the electrophile. The AlCl3 pulls
the Cl away from the haloalkane:
After the electrophile is generated, the electrophilic substitution reaction can take place exactly as
described in part 1.

after alkylation the benzene ring becomes more activated/reactive (due to the presence of an
electron donating alkyl group) towards electrophiles so further substitution can be a problem.

Acylation
Friedel-Crafts acylation is very similar to the alkylation reaction, but with the addition of a carbonyl group.

We start off with an acyl chloride, for example:

You then simply proceed similarly to the alkylation reaction by reacting the acyl chloride with a halogen
carrier to generate the electrophile:

the acylation product shown below is more versatile than an alkylation product. You can now do
nucleophilic reactions at the carbonyl group, which is an exam favourite.

The acylation product is also more stable than the alkylation product making it easier to control in the
laboratory, meaning further substitution is unlikely to happen.

Halogenation
This is very similar to the Friedel-Crafts stuff. A halogen carrier such as FeBr 3 or AlCl3 is again used to
polarise Br2 or Cl2 enough to generate the Br+ or Cl+ nucleophile.

AlCl3 + Cl2 AlCl4- + Cl+

I have also seen questions where they start from Fe. They would do something like:
2Fe + 3Br2 2FeBr3
FeBr3 + Br2 FeBr4- + Br+

with Friedel-Crafts and halogenation reactions you can show the catalyst being regenerated similarly
to that shown for the nitration example.

AlCl4- + H+ AlCl3 + HCl

Other Reactions

Hydrogenation
As we saw in part 1, benzene can be hydrogenated by addition of H2/Ni catalyst. This can be viewed as
reduction as hydrogen is being added.

this is not electrophilic substitution. We have actually added not substituted.

Combustion
Benzene can be combusted just like any hydrocarbon CO2 + H2O. A smoky flame is usually seen.