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Author: Subject: Methylene Dioxy Phenyl Propyl Piperidine.
chemist1243
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[*] posted on 9-12-2019 at 09:02
Methylene Dioxy Phenyl Propyl Piperidine.


so in a previous thread, i discussed adding a piperidine ring to safrole, but my plan was poorly thought out. i have since developed a new route for the synthesis of this compound.

here's the BASIC overveiw:

first, we brominate safrole using Br2 and FeBr3 catalyst to get bromosafrole. from there we react the bromosafrole with ammonia to get the amine; MDA.

the MDA is reacted with hydrazine to yeild methylene dioxy phenyl propyl hydrazide.

then we convert this to the azide using nitrous acid solution(NaNO2 in 0C HCl).

finally, the resulting azide is reacted with piperidine to yeild methylene dioxy phenyl propyl piperidine.


what you guys think?

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Sigmatropic
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[*] posted on 9-12-2019 at 09:35


First, ring bromination is likely with the Lewis acid present. Also you'd get the vicinal dibromide from an alkene.

Second, unprecedented reaction. That's not a (general) way to make alkyl hydrazines. But maybe I'm wrong?

OK to the azide, to do what? Use it as a pseudo halogen leaving group? That's 4 steps to get back to where you were... And with a worse leaving group. I just don't see the logic behind that.

Just for your information there are reagents out there that convert amines into azides, known as diazotransfer reactions.
But I don't see how the azide is relevant at all...

Edit: what's the propose of this theoretical excersize? Going towards a product? Or coming from a starting material?

For practice in retrosynthetic analysis, I 'd suggest picking a different structure, take a look at https://www.drugs.com/newdrugs.html and pick any which doesn't end in -mab, short for monoclonal antibody, they're not produced by chemical synthesis so not so useful for this excersize. So two of them would be: https://en.m.wikipedia.org/wiki/File:Voxelotor_skeletal.svg
And
https://en.m.wikipedia.org/wiki/File:Cenobamate.svg

In this way you end up with modern chemistry, not the 1960 style chemistry as an answer...

[Edited on 9-12-2019 by Sigmatropic]
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Corrosive Joeseph
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[*] posted on 9-12-2019 at 12:55


Am I missing something here......? What is wrong with KOH isomeration --> performic oxidation --> reductive amination with piperidine.


/CJ




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chemist1243
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[*] posted on 9-12-2019 at 13:30


Quote: Originally posted by Sigmatropic  
First, ring bromination is likely with the Lewis acid present. Also you'd get the vicinal dibromide from an alkene.

Second, unprecedented reaction. That's not a (general) way to make alkyl hydrazines. But maybe I'm wrong?

OK to the azide, to do what? Use it as a pseudo halogen leaving group? That's 4 steps to get back to where you were... And with a worse leaving group. I just don't see the logic behind that.

Just for your information there are reagents out there that convert amines into azides, known as diazotransfer reactions.
But I don't see how the azide is relevant at all...

Edit: what's the propose of this theoretical excersize? Going towards a product? Or coming from a starting material?

For practice in retrosynthetic analysis, I 'd suggest picking a different structure, take a look at https://www.drugs.com/newdrugs.html and pick any which doesn't end in -mab, short for monoclonal antibody, they're not produced by chemical synthesis so not so useful for this excersize. So two of them would be: https://en.m.wikipedia.org/wiki/File:Voxelotor_skeletal.svg
And
https://en.m.wikipedia.org/wiki/File:Cenobamate.svg

In this way you end up with modern chemistry, not the 1960 style chemistry as an answer...

[Edited on 9-12-2019 by Sigmatropic]


So if ring bromination would be one of the major concerns, let’s just find another aromatic and brominate that, and then use the left over HBr generated from that to brominate the safrole?
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Sigmatropic
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[*] posted on 9-12-2019 at 13:53


Quote: Originally posted by Corrosive Joeseph  
Am I missing something here......? What is wrong with KOH isomeration --> performic oxidation --> reductive amination with piperidine.


/CJ


Or Wacker oxidation and reductive amination with piperidine...
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draculic acid69
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[*] posted on 9-12-2019 at 16:07


None of that sounds correct.
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clearly_not_atara
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[*] posted on 9-12-2019 at 16:12


If you can make 5-iodobenzodioxole, conversion to the diaryliodonium salt allows an easy Stork enamine reaction with the piperidine imine of acetone, which give 1-benzodioxol-5-yl-2-piperidin-1-ylpropene, which can be subsequently reduced to the target compound.


[Edited on 10-12-2019 by clearly_not_atara]




[Edited on 04-20-1969 by clearly_not_atara]
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dextro88
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[*] posted on 10-12-2019 at 06:38


Quote: Originally posted by chemist1243  
so in a previous thread, i discussed adding a piperidine ring to safrole, but my plan was poorly thought out. i have since developed a new route for the synthesis of this compound.

here's the BASIC overveiw:

first, we brominate safrole using Br2 and FeBr3 catalyst to get bromosafrole. from there we react the bromosafrole with ammonia to get the amine; MDA.

the MDA is reacted with hydrazine to yeild methylene dioxy phenyl propyl hydrazide.

then we convert this to the azide using nitrous acid solution(NaNO2 in 0C HCl).

finally, the resulting azide is reacted with piperidine to yeild methylene dioxy phenyl propyl piperidine.


what you guys think?



You really think to Aminate Safrole, have you tried that, and why you woud aminate the bromosafrole with amonia, and then rearange to the N-Piperdine analog, since you can directly do the amination with piperidine ? Im intrested what kind of reserach are you doing and isnt this theard a litle bit Detritus ?
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chemist1243
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[*] posted on 15-12-2019 at 09:52


Quote: Originally posted by dextro88  
Quote: Originally posted by chemist1243  
so in a previous thread, i discussed adding a piperidine ring to safrole, but my plan was poorly thought out. i have since developed a new route for the synthesis of this compound.

here's the BASIC overveiw:

first, we brominate safrole using Br2 and FeBr3 catalyst to get bromosafrole. from there we react the bromosafrole with ammonia to get the amine; MDA.

the MDA is reacted with hydrazine to yeild methylene dioxy phenyl propyl hydrazide.

then we convert this to the azide using nitrous acid solution(NaNO2 in 0C HCl).

finally, the resulting azide is reacted with piperidine to yeild methylene dioxy phenyl propyl piperidine.


what you guys think?



You really think to Aminate Safrole, have you tried that, and why you woud aminate the bromosafrole with amonia, and then rearange to the N-Piperdine analog, since you can directly do the amination with piperidine ? Im intrested what kind of reserach are you doing and isnt this theard a litle bit Detritus ?


true. i wasnt sure how animations secondary amines could affect my final product, but i knew that methylamine or ammonia would work, so i decided that NH3 would do fine. i also knew that primary amines could be reacted with hydrazine to get the hydrazide, and then reacted with Nitrous acid(in the form of NaNO2 in acidic solution) to yeild an azide. this azide could then be reacted with a secondary amine to get the disered product. if it would truly be more doable to just skip all of the hydrazide/aide steps and whatnot, then i see a reaction with a secondary without the extra clutter would be feasable.
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[*] posted on 17-12-2019 at 20:02


There are hypothetically bioactive 3-amino-1-propiophenones. They could be reached by reaction of the substituted propiophenone with paraformaldehyde and your amine hydrochloride (piperidine in this case). It is a Mannich reaction. Compounds of this structure might be interesting, but also this ketone might possibly be useful as an intermediate to your desired phenylpropylpiperidine compound. This would of course be predicated upon your having access to 3,4-methylenedioxypropiophenone.

edit: now that I more thoroughly read the thread, it seems the compound you want to produce is 3,4-methylenedioxyphenyl-prop-2-piperidin-ane (my IUPAC is not strong). This would be reductive amination of the phenyl-2-propanone with piperidine as your amine base.

interesting structure.
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