In the previous video we prepared what we believe to be crude manganese 3 acetate.

It's a fine reddish-brown colored powder as you can see here.

Since manganese 3 is easily reduced to manganese 2 with the gain of a single electron,

it can apparently generate an acetate radical, which has the ability to enable some unusual reactions.

We're going to try this out in this video.

We're starting here with 25 grams of the manganese 3 acetate that we prepared earlier and which was dried over calcium oxide for a week.

We're going to use a 250 milliliter flask for this.

For the reaction, equipped with a magnetic stir bar as an inert solvent for the reaction to take place,

we've measured out 50 mils of petroleum ether.

And now for our first reactant.

We're going to use a more electrophilically active compound to stand the best chance of reacting.

So this is 5.8 grams of manganese 3 acetate.

This goes into the flask too.

Now we're stirring vigorously and we're going to add the manganese 3 acetate to the flask.

It sinks to the bottom but doesn't clump together and the mixture is still able to be stirred.

Here we are on complete addition.

Now we start heating the mixture up to a reflux.

Our pet ether should boil between 60 and 90 degrees.

We've got a small e-big condenser attached to the top of the flask with some cold cooling water to help the mixture reflux.

Okay this is going nice out and we've got a good reflux.

And as a result quite a bit of mixing of the solid in the flask with the pet ether and anisole.

It's interesting that we recall reading a literature claim that a brown solution is formed.

But we can see that the brown manganese 3 acetate has any solubility in organic solvents apart from in acidic acid.

Here's our final reactant.

This is 10 mils of dry acetone, which is about a 2.5 stoichiometric excess of the anisole.

This is added through the condenser into the reaction flask.

And now we're going to keep stirring and occasionally agitating the flask to make sure it's all mixed up.

And we keep the mixture refluxing for the next 4 hours.

It might just be wishful thinking, but it looks as though it's turning asleep.

slightly more red-brown color.

Unfortunately our condenser isn't very efficient,

so over the four hours we're steadily losing some of the pet ether solvent.

Here we are four hours later.

A big mass of congealed solid in the bottom of the flask.

We let the flask cool down to room temperature,

and then we transferred the contents into a filter center.

We decided to use dichloromethane as a solvent,

with the best chance of extracting everything there was to be had out of the mixture.

So we washed the reaction flask with DCM and then poured into the filter.

Once dry, we switched off the pump and used another portion of about 30 ml of DCM

to wash the solids in the filter carefully.

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We repeated this again to ensure we extracted all organic material.

Here's the filtrate we collected.

It's a dirty brown color as you can see.

This probably contains some acetic acid, water and possibly some inorganic impurities.

So we poured it into a separating funnel.

And added 40 ml of cold water to see if this would clean our organic layer.

On vigorous shaking we've got a brown aqueous layer on top,

and a pale yellow colored organic layer below.

So we separated off the bottom organic layer.

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lithium sulfate.

Okay so let's distill and find out what we're got in here apart from pet ether and DCM.

We've got a thermometer so we can record the temperature of the liquid vapors.

The solvents come off pretty quickly and easily.

Pretty soon we're down to a small amount of oily liquid remaining in the boiling flask.

We continue the distillation to make sure that we've got all of the solvents

remaining.

So we've recovered our pet ether and DCM here in the receiving flask.

And here's our non-volatile remaining component.

About five mils of pale yellow liquid.

And it has the telltale characteristic unmistakable smell of, yes you guessed it, anisole.

Nothing else.

Nothing exotic.

Just anisole.

Just to test, we make up a saturated solution of sodium bisulfite in about 30 mils of water.

Now let's add the product.

But even with lots of stirring and mixing there's no sign of any adduct forming, on

even a tiny scale.

Well.

We've got our anisole back and it shows that our extraction worked.

If there was any product in that reaction mixture we would have it right here.

But there isn't.

So our first test of this reaction is a negative.

We decided then to see if it was possible to recrystallize some of our suspected manganese

3 acetate using about 30 mils of hot acetic acid.

it turns out to be incredibly soluble so much so that it's impossible to tell

when a saturated solution exists perhaps missable is the right word to use we've

dissolved about 20 grams and we've got a slightly syrupy liquid either the

product is in solution or it's suspended in there we can tell so we first allowed

this mixture to cool to room temperature but all that resulted was a slightly

liquid even on chilling no solids separated so we decided to adjust the

polarity of the mixture by adding petroleum ether we added quite a bit

until the total volume was about 150 mils to see if this would help something

precipitate or crystallize out after 12 hours there was a gloopy thick brown

liquid at the bottom of the beaker so we put the mixture in the freezer

at minus 10 degrees C for another 24 hours and we've got a solid formed so we filtered this off

We washed with a little dichloromethane, but this may have been a mistake because it looks as though the solid is far more soluble in this than it is in PET ether

On drying we got a good proportion of our brown cinnamon colored solid back again

Overall very strange behavior, but gives us some more clues

Okay so now for our second attempt

Let's see if the drying of the material somehow rendered it inactive as it seems to emit acetic acid vapors even after wash repeatedly with solvent

So we prepared a fresh batch of manganese 3 acetate, but instead of drying over calcium oxide, we washed it with diethyl ether to remove excess acetic acid

Here's the solid with a small amount of ether and acetic acid still present

We decided to use the entire batch containing the acid

And theoretically just over 36 grams of manganese 3 acetate dihydrate in our next experiment

Here's a 250 ml flask with stir bar

Let's get our manganese 3 acetate starting compound in here

We decided on this run not to use a solvent

Instead we'll use anisole as before as it stands a better chance of undergoing reaction

And an excess of acetone

Here's 5 grams of anisole

We place this into the flask

And now here's 60 ml of dry acetone which is a potential reactant, but present in excess to act as a solvent

This goes into the flask

So as before, we refluxed this mixture for 3 hours in total

There wasn't much visible change in the reaction mixture over this time as you can see

Then we allowed to cool and filtered the reaction mixture through a glass center to remove the brown solids

We washed out the flask with dichloromethane and used this to wash the solids in the filter

Interestingly the solids have reduced in volume from our starting material and are black like precipitated manganese dioxide

They also don't form a brown solution in water

We transferred the filtrate into a separating funnel

Interestingly, on standing some colorless crystals formed in the filtrate

We dissolved these in a little water, and then added this aqueous mixture to the funnel

We then shook the mixture to ensure any inorganic products were transferred to the aqueous layer

We've got two layers now, the bottom one being our dichloromethane solution

We separated this bottom layer off and washed the residual aqueous layer with another portion of dichloromethane to remove as much organic product as possible

Here's the organic layers combined and drying over anhydrous magnesium sulfate

So just as we did before

In order to remove the solvent and see what we've got in there

First of all the dichloromethane comes off

We recovered most of this

Then we got some acetone coming off up to about 100 degrees C

Then the distillation slowed right down and we got a small amount of water coming off

But combined with something steam distilling

The mixture was thoroughly dried, so we're not sure how this is possible

Some sort of decomposition perhaps

After a while a white solid started to form in the boiling flask

So we decided to add some water and then we steam distilled the mixture to get any organic contents off

In the boiling flask we're left with an aqueous mixture with a faint aroma of pineapples

And here's our steam distillate containing an oily top layer of organic product

And just like before, this appears to be just anisole

There's no ketones in here

Well, it's been fun and although we've not managed to get this to work

There are a lot of open questions

The second reaction did seem to do something

But we don't have the analytical equipment to find out what

We'll keep experimenting with this and we'll let you know in the future if we ever get any conclusions

Thanks for watching and stay tuned

Thanks for watching and stay tuned