Author Topic: A new Friedels-Craft Route to substituted Propenylbenzenes?  (Read 188 times)

ausser_betrieb

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A new Friedels-Craft Route to substituted Propenylbenzenes?
« on: May 18, 2010, 06:38:53 PM »
FCA is favorable over Grignard, no need for Mg and no Bromination, but where to get water-free AlCl3? Also the highly acidic Conditions tend to mess up some substituions. The new research showing that Graphite can substitute Lewis Acids (note that there are no acidic conditions involved now!) - with the drawback that only carboxylic acid halogenids work. So what to do with this extra oxygen? Acryliy acid halogenid and reduction? Reducing the Oxygen completly isnt really an option IMHO. So why not use Propionic acid chloride, reduce the Ketone to the alcohol, then dehydrate to the propenyllbenzene. The reduction to the alkohol could be done in good yields with electrolysis.

Please let me hear you opinion (also, if you have refs with details on the electrolytic reduction - feel free to contribute)
« Last Edit: May 18, 2010, 06:41:08 PM by ausser_betrieb »

Evilblaze

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Re: A new Friedels-Craft Route to substituted Propenylbenzenes?
« Reply #1 on: May 18, 2010, 09:13:33 PM »
The acylation part of this writeup is working in really-really good yields. There will be no problem with is. As you can see the recipe below, with not so hard conditions the propionyl chloride will react with the aromatic substance. And because of the anisole-s highly activated aromatic ring, you don't have to use so much AlCl3 or you can use some other, weaker lewis acids.
The selectivity of the acylation is a good question. If toluene is used, than only the para isomer will form. If anisole... good question.

Quote
Preparation of 4-methylpropiophenone

 
73g aluminium chloride
300mL dichloroethane
46mL propionyl chloride
54mL toluene
600mL iced water
200mL 5% NaOH solution
Magnesium sulfate

54mL (500mmol, 46g) toluene was added over 30 minutes to a solution of 73g (550mmol) anhydrous aluminium chloride and 46mL (525mmol, 49g) propionyl chloride in 200ml dichloroethane cooled via an external ice bath. The solution was allowed to stir for a further 1.5 hours at 20oC, and was then carefully added to 500mL stirred iced water. The lower dichloroethane layer was separated off, and the aqueous layer extracted with 2x50mL dichloroethane. The combined extracts were washed with 2x100mL 5% NaOH, 100ml water, and then dried over magnesium sulfate. The solvent was removed, and the ketone vacuum distilled at 123-126oC, to give 1-(4-methylphenyl)-propan-1-one as a colourless oil.
Yield: 70.0g (95%)

The other reactions will go, there will be no problem with it. The hydrogenation can go with almost anything what won't reduce the oxo group to alkane. And the last step... Get a good reference for it.

I hope I helped a bit.

ausser_betrieb

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Re: A new Friedels-Craft Route to substituted Propenylbenzenes?
« Reply #2 on: May 19, 2010, 08:27:19 AM »
@Evilblaze, the point was not to use AlCl3, but graphite.

Enkidu

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Re: A new Friedels-Craft Route to substituted Propenylbenzenes?
« Reply #3 on: May 19, 2010, 08:56:57 AM »
The new research showing that Graphite can substitute Lewis Acids (note that there are no acidic conditions involved now!) - with the drawback that only carboxylic acid halogenids work.

That's not true, acids will work as well, but they require different rxn conditions, namely a strong acid. Sorry, don't have the ref with me.

Evilblaze

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Re: A new Friedels-Craft Route to substituted Propenylbenzenes?
« Reply #4 on: May 20, 2010, 12:04:35 AM »
Graphite also works. Just...

Usually graphite is used as a Friedel-Crafts reaction catalysts when the acylating reagent has a higher boiling point and it is an acid-bromide and not chloride. With chlorides it also works, but the yield won't be so good.

There is another problem. The amount of the reactants. What I found reference, the whole reaction setup was only 3-5g. Not so much. And really much graphite was needed and relative long heating.

Quote
In a typical experiment, graphite was
added to a mixture of anisole (2 mmol) and benzoyl bromide (3
mmol) in benzene. The mixture was heated under reflux for 8 h.
....
The amount of
graphite used relative to benzoyl bromide was between 0.5 and
2 g.

The other problem is the graphite. The graphite what was used here, was from Sigma-Aldrich. It was Graphite powder, <20 um. This is so small mesh what can't just made at home easily. The net catalog number of the required graphite: 282863

So:
The reaction of anisole and propionyl chloride will have a really low yield, because the propionyl chloride has a low boiling point, so it is not an "optimal" reactant and it is a chloride and not a bromide, so it is much less reactive.
And if you want to scale up the reaction, don't be surprised if the not so high yields will start to decrease. 

There are several Lewis acids what are much more easily obtained and because of the anisole-s high activity they will produce a fairly good yield. Example FeCl3 or SnCl4. Cheap as dirt and good for friedel-crafts reaction.

Think it again.

Vanadium

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Re: A new Friedels-Craft Route to substituted Propenylbenzenes?
« Reply #5 on: May 20, 2010, 01:00:57 AM »
I'm more concerned about the availability and manufacturability of acid chlorides, specifically propionic acid. I know the ref of which Enkidu speaks but it required superacids (tosic, triflic, maybe even magic) that are not available to the clandestine chemist. "Chuck a bunch of sulfuric acid in there" isn't likely to work either, but feel free to prove me wrong; we've all got an activated aromatic, H2SO4, AcOH, and bisulfite (to check for ketone products) laying around. ;)

Enkidu

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Re: A new Friedels-Craft Route to substituted Propenylbenzenes?
« Reply #6 on: May 20, 2010, 04:32:10 AM »
Solvent-Free Catalytic Friedel - Crafts Acylation of Aromatic Compounds with Carboxylic Acids by Using a Novel Heterogeneous Catalyst System: p-Toluenesulfonic Acid/Graphite
Mona Hosseini Sarvari and Hashem Sharghi
Helvetica Chimica Acta Volume 88 Issue 8, Pages 2282 - 2287 doi:10.1002/hlca.200590162

Abstract: TsOH/graphite was found to be an effective catalyst system for the Friedel-Crafts  acylation of aromatic compounds with carboxylic acids. Both aliphatic and aromatic carboxylic acids reacted smoothly under TsOH/graphite catalysis to afford the corresponding aromatic ketones in high yields. The graphite was easily recovered by simple extraction and could be reused without decrease of activity in the presence of fresh TsOH.

Enkidu

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Re: A new Friedels-Craft Route to substituted Propenylbenzenes?
« Reply #7 on: May 20, 2010, 06:37:51 AM »
it required superacids (tosic, triflic, maybe even magic) that are not available to the clandestine chemist.

Tosylic acid isn't a superacid, is it? and it's definitely one prep away from OTC reagents in the US.

Vanadium

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Re: A new Friedels-Craft Route to substituted Propenylbenzenes?
« Reply #8 on: May 21, 2010, 06:32:49 PM »
Tosylic acid isn't a superacid, is it? and it's definitely one prep away from OTC reagents in the US.

Huh. Coulda sworn it was. :/ Anyway, I at least remember another paper where they (same authors? Hosseini's dissertation on related topics is somewhere out there on the internet if you're curious) tried using H2SO4 and got very poor yields. I might post it here if I have the time to find it again.

Enkidu

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Re: A new Friedels-Craft Route to substituted Propenylbenzenes?
« Reply #9 on: May 21, 2010, 07:25:42 PM »
Will you please post that dissertation? I would be very interested in reading it. I searched for it using my library's dissertation database, but I couldn't find it.

Vanadium

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Re: A new Friedels-Craft Route to substituted Propenylbenzenes?
« Reply #10 on: May 23, 2010, 04:37:14 AM »
Will you please post that dissertation? I would be very interested in reading it. I searched for it using my library's dissertation database, but I couldn't find it.

I searched for it and couldn't find it, though I distinctly recall reading it. Most of the information in there can be found via her publications page (lots of interesting, clandestinely-relevant material on here):
http://research.shirazu.ac.ir/faculty/More.asp?ID=664