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Today we're going to do a two step reaction, starting with benzyl

chloride, reacting this to form benzyl cyanide, and then hydrolysing this
to form phenylacetic acid.
The first step in this process to form benzyl cyanide is one we've
actually done before in a previous video, but this time we're going to try
a different procedure to see if we can get a cleaner product.
Here's our starting materials for the first step of the reaction sequence.
Let's go through these.
First up is our benzyl chloride. We're trying the new process out on a
small scale so we've weighed out 4 grams of liquid benzyl chloride. We've
prepared this in a previous video from benzyl alcohol, so check it out at
the link shown if you want more information. It's a very unpleasant
compound, so do minimise your exposure as much as possible.
Reacting with this we have our alkali cyanide salt. Here we've weighed out
2.8 grams of mixed sodium-potassium cyanide which contains these in a 1to-2 molar ratio.
We prepared this in a previous video using anhydrous potassium
ferrocyanide and sodium metal, and dehydrating the aqueous solution using
absolute ethanol. Have a look for more details.
Alkali cyanides are extremely toxic and will kill you rapidly, so take
great care with handling them. Make sure they never come into contact with
acidic compounds or deadly hydrogen cyanide gas can be generated.
And finally our catalyst for the reaction. This is 0.3 grams of sodium
iodide crystals. Our understanding is that potassium iodide unfortunately
won't substitute here, but it might be worth a try anyway!
We'll perform the reaction in a 100 mill flask which is set up on a hot
plate, and you'll need good magnetic stirring to do this properly.
Use ventilation as well because you don't want to risk it with alkali
cyanide in here and with very unpleasant benzyl chloride as well.
Let's get our dry starting materials into the flask first. The sodium
iodide. And the sodium potassium cyanide.
And next we'll add the benzyl chloride.
As a solvent we're going to use a mixture of 15 mills of acetone and 5
mills of absolute ethanol. First we'll use this to wash the beaker which
contained the benzyl chloride. Then we get the rest in.
Ok we're now ready, so first of all let's get the stirring going fairly
vigorously.
And now we set up for
condenser in order to
Let's get heating the
we'll keep this going

reflux. You'll need to use fairly cool water in the


stop the acetone vapour from slowly escaping.
mixture until we've got a gentle reflux. And now
for the next 3 hours.

So what's happening in this first reaction step. Well cyanide ions are
very good nucleophiles, and will attack carbon atoms in other compounds
where they can displace a good leaving group.
In this case we've got benzyl chloride which has a carbon with a chlorine
atom bonded to it. The cyanide can attack the carbon and kick out the
chlorine atom as a chloride ion.
And so we end up creating our product, benzyl cyanide. In doing so we've
effectively added an extra carbon atom onto the molecule from the cyanide.
The sodium iodide acts as a catalyst because in acetone it's able to form

benzyl iodide as an intermediate, and iodide is an even better leaving


group than the chloride. The iodide is regenerated in the process.
The colour and texture of the solid in the flask seems to change over the
3 hours to a more granular and whiter coloured solid.
We stop heating and stirring and allow the mixture to cool. And now let's
filter. We washed the flask and the solids with 10 mills of acetone.
So let's transfer the filtrate containing the phenylacetonitrile into a
flask. The aroma has changed and there's no more irritating benzyl
chloride present.
So now we're going to set up for distillation and remove the solvent from
the filtrate. Interestingly it's quite a pale coloured mixture, unlike the
orange to dark brown coloured mixture you get using the previous method we
tried.
We've got the solvent distilling off nicely now. And pretty soon it's all
off. At the end of the distillation a yellow oily liquid remains in the
flask. With the characteristic slightly pongy aroma of phenylacetonitrile,
otherwise known as benzyl cyanide. There's a little bit of water as well
as you can see.
Ok we're going to move right on to the next step of the reaction, which is
to hydrolyse this nitrile to the corresponding carboxylic acid.
To do this we're going to use 10 mills of 50% by volume sulfuric acid.
We've set the flask back up with a reflux condenser again. So let's add
the acid. And closed back up. And now we'll heat and stir the mixture.
Hydrolysis of the nitrile to the acid should be pretty rapid. Once the
mixture reached reflux temperature we kept it there for one hour. The
colour of the mixture turned orange as it was heated. You can see that the
non-aqueous component is getting darker.
So let's leave this for an hour. Let's also have a look at what's
happening in this second part of the reaction.
Organic nitriles and in fact alkali cyanide salts are easily hydrolysed
both in acidic and alkaline solution. Let's look at the acid hydrolysis
that's occuring in this reaction.
First of all the nitrile is protonated, leading to a more electrophilic
carbon in the nitrile group. This is then attached by water as the
nucleophile. The resulting species fairly easily loses and proton and then
rearranges to form an intermediate hydrolysis product, an organic amide.
And as you know, amides can also be hydrolysed in a similar way. The
oxygen in the carbonyl group of the amide is protonated, leading to a
species which just like before ends up getting attacked nucleophilically
by a water molecule.
The resulting species then eliminates ammonia to form the product, a
carboxylic acid.
As you can see the colour of our reaction mixture is turning darker. And
after an hour of refluxing it looks like this. So we stop stirring and
allow to cool.
There's a dark red brown coloured organic layer and a yellow coloured
aqueous layer. This actually looks very similar to the product you get

when you hydrolyse benzyl cyanide made by the other method we tried
previously.
Ok this is chilled down now, and the reaction mixture has a very strong
sweet acacia honey like aroma. Phenylacetic acid. So there's definitely
some in here, we now need to get it out.
So here's 10 grams of solid sodium hydroxide. Enough to completely
neutralise all sulfuric acid, and also convert all phenyacetic acid into
the sodium salt. We used a couple of ice cubes and a little water to make
up a cold solution.
Ok let's add the reaction mixture. Well, if there was a lot of
phenylacetic acid in here we'd get a solid crystallising out, but it
doesn't always happen.
Let's check the pH first and make sure that the mixture is strongly
alkaline.
It is, and what this means is that any phenylacetic acid should be
dissolved in our aqueous solution as sodium phenylacetate now.
Here's our mixture. It's cleared up a bit, but there's some brown organic
impurities floating on the top still. Let's get this into a separating
funnel.
And now we're going to add 10 mills of dichloromethane to the mixture
which should hopefully dissolve out the organic byproduct materials. Ok
after a good shake, let's see where the brown goes. It's going into the
bottom DCM layer, which is good.
And our aqueous layer is looking quite clean. So let's drain off the DCM
layer. Ok great. We repeated the process with another 10 mills of DCM just
to clean up a bit more. And now all the impurities, starting materials,
and brown colour is in the DCM extract.
Let's separate the aqueous layer now. Ok well to get our phenylacetic acid
out we'll need to acidify the mixture, so here's about 12 mills of
concentrated hydrochloric acid.
Let's just confirm the pH of the mixture is now strongly acid.
Now we'll get the mixture into a separating funnel. It's murky looking and
there are some drops on the surface so it looks like there's some product
in here, but not that much.
We'll use a couple of portions of 10 mills of DCM to extract this. We
shake vigorously and allow to separate. And now we'll drain off the bottom
DCM layer. We repeated the extraction with another 10 mills of DCM. Then
dried the combined DCM extract using some anhydrous magnesium sulfate.
Ok let's evaporate the DCM solution down and see what we've got. And here
we go. There's some oily residue left in the petri dish as you can see.
And on cooling this crystallises forming an off-white solid with a very
potent strong petro-chemical honey aroma. A bit like a form of artificial
fake honey flavouring.
Well we can scrape up some very crude product from here. If we do this
then we've got about half a gram of product.
A bit disappointing really. There's not much that can go wrong in the
second hydrolysis step, so this means that the product of the first

reaction only contained a small amount of phenylacetonitrile


unfortunately.
So our recommendation if you want to do this reaction is to use the more
classic method of reacting benzyl chloride and sodium cyanide together in
a water and ethanol solution. We covered this in a previous video so take
a look. This gives reasonable yields of phenylacetic acid when hydrolysed.
It may also be that we simply didn't reflux the mixture for long enough,
but who knows.
Another option is to produce mandelic acid and then reduce this, but this
is a bit more complex. We also covered this in a previous video so take a
look for more details.