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Author: Subject: Methylenedioxy-substituted Propiophenone
TurbineTreasure
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[*] posted on 8-10-2014 at 14:31
Methylenedioxy-substituted Propiophenone


Not looking to be spoon fed, but I would be extremely interested to see if this particular species of aryl ketone can be used to produce propenylbenzene, specifically isosafrole.

I have searched this site, google, all of the sites that shall remain nameless that usually discuss this type of thing (you know which ones I'm talking about), as well as the literature for an example using the MD-substituted version, but to no avail. If anyone here can at least shove me in the right direction it would be much appreciated.

Either I am just not as good at patent hunting as I thought I was, or this particular endeavor must be uncharted territory, at least from the 3,4 MD side of things.

[Edited on 8-10-2014 by TurbineTreasure]
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Chemosynthesis
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[*] posted on 8-10-2014 at 15:35


Normally I refrain from posting much on these types of topics, but I appreciate your candor and observance of forum decorum. I have no examples, but very strongly suspect it can be done without compromising the methylenedioxy bridge, in addition to two other plausible routes to what I presume is your target compound, but I am not sure why anyone would want to go out of their way for this other than reaction novelty due to the precursor's use in methylone synthesis undoubtedly raising red flags in most regions MDMA is illicit.
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Crowfjord
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[*] posted on 8-10-2014 at 15:45


Seems like pretty rudimentary stuff, to me. Maybe there aren't references to the specific compound, but related ones should be out there. Why not reduce the ketone to a benzyl alcohol and then eliminate water to form the alkene? There should be references out there for those simple reactions, many of which I'm sure wouldn't mess with the heterocycle.
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TurbineTreasure
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[*] posted on 8-10-2014 at 16:01


An appreciation for novelty routes as much as an aversion to EtNO2 prep is what lead to these questions. I am aware of a multitude of routes to the target molecule, but this one seems like the least-trodden path. Never being one to shy away from learning or hard work, I am interested to say the least. Anyone can acquire precursor 1 and precursor 2 and "cook" themselves up a hefty prison sentence. Lest we forget, this is about the chemistry ladies and gentlemen.

I did have a feeling that the MD bridge could possibly survive the established routes for unsubstituted propiophenone. But without a known example using the 3,4 variant, it looks as though it's time for some experimental preparatory exercises to commence.
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TurbineTreasure
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[*] posted on 8-10-2014 at 20:52


Actually, that route is also of interest...

If possible, would the sacrifice of the high-yielding procedures normally followed using borohydrides to reduce ketones to alcohols, perhaps be replaced with the Zinc/sodium hydroxide system employed by Vogel in the preperation of diphenylcarbinol?

Honestly, the viabilty of the heterocycle in question is of concern here as well.


[Edited on 9-10-2014 by TurbineTreasure]
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palladium8
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[*] posted on 17-10-2014 at 22:43


Wacker oxidation of isosafrole should give a mixture of (3,4-methylenedioxy)phenyl-1-propanone and the 2-propanone—overwhelmingly the 1-propanone product though.

But for total synthesis:
1. (3,4-methylenedioxy)phenylmagnesium bromide + propanal
2. Oxidation with potassium dichromate to yield (3,4-methylenedioxy)propiophenone

[Edited on 18-10-2014 by palladium8]
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TurbineTreasure
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[*] posted on 18-10-2014 at 11:51


Very good, but I was more concerned with the synthesis of a propenylbenzene from a propiophenonein regards to the 3,4-methylenedioxy variant. Not the other way around.

I guess I should change the thread title to "5-(1-Propenyl)-1,3-benzodioxole from 5-Propionyl-1,3-benzodioxole" Any idea how to change titles of threads? I'm new here.

I like the route through the alcohol as stated by Crowfjord, but the only experimental I could find regarding the 3,4-MD version was an unreferenced lab manuscript that used the methoxy version, but theorized the methylenedioxy bridge would fare just as well through the treatment with borohydride, and subsequent treatment with KHSO4.

I'm just looking for a precedent here for actual proof before it is attempted.





[Edited on 18-10-2014 by TurbineTreasure]

[Edited on 18-10-2014 by TurbineTreasure]
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