Sciencemadness Discussion Board
Not logged in [Login ]
Go To Bottom

Printable Version  
Author: Subject: 3,4methylendixoytoulene to ketones
dextro88
Harmless
*




Posts: 35
Registered: 20-10-2018
Member Is Offline


[*] posted on 12-1-2020 at 10:01
3,4methylendixoytoulene to ketones


Hello everybody recetly i obtained a kilo of this fruitty smelling stuff and i am wiling to experiment, and tried a micro scale reaction to synthesis 5-methyl-3,4methylendioxyvalerophenone using valeric acid and polyphosphoric acid as catalysts and it worked with high yield, today i tried to prepare the 5-methyl-Safrole with allyl alcohol and PPA as catalyst and 5-Methyl-benzodioxole, mixed the allyl alcohol with the catalyst and the hydrocarbon was added with pressure funel overtime with cooling bath controling the reaction tempreture not go over 20C until all the hydrocarbon added than heated to 80C for 2 hours, poured into hcl/ice/water solution and stired overnight, the non-polar layer extracted and upon destilation i dont received any ketone, only recovered the hydrocarbon or atlest somethink with very low boiling point wich for shure isnt my ketone and smells like my starting material, isnt PPA suitable for synthesis of allylbenzenes ? What catalyst woud you recomend to use ?



[Edited on 12-1-2020 by dextro88]
View user's profile View All Posts By User
draculic acid69
International Hazard
*****




Posts: 789
Registered: 2-8-2018
Member Is Offline


[*] posted on 14-1-2020 at 18:21


You added an alcohol to the rxn instead of an carboxylic acid meaning you won't get a ketone.
View user's profile View All Posts By User
dextro88
Harmless
*




Posts: 35
Registered: 20-10-2018
Member Is Offline


[*] posted on 15-1-2020 at 02:44


why i buy a lot of the allyl alcohol for this job, there is a lot of papers preparing allylhydrocarbons using FC and allyl alcohol with a lewis acid catalyst ?
View user's profile View All Posts By User
draculic acid69
International Hazard
*****




Posts: 789
Registered: 2-8-2018
Member Is Offline


[*] posted on 15-1-2020 at 04:49


Maybe polyphosphoric acid only works on carb acids to ketones not as a Lewis acid replacement for the allyl alcohol FC rxn. Try anhydrous alcl3 instead.
View user's profile View All Posts By User
dextro88
Harmless
*




Posts: 35
Registered: 20-10-2018
Member Is Offline


[*] posted on 15-1-2020 at 07:19


why it dont work ? The Alcl3 will mess with the MD bridge and produce mostly tar...
View user's profile View All Posts By User
Tsjerk
International Hazard
*****




Posts: 1995
Registered: 20-4-2005
Location: Netherlands
Member Is Offline

Mood: Mood

[*] posted on 15-1-2020 at 09:36


Quote: Originally posted by dextro88  
why i buy a lot of the allyl alcohol for this job, there is a lot of papers preparing allylhydrocarbons using FC and allyl alcohol with a lewis acid catalyst ?


Do you have one of these references?
View user's profile View All Posts By User
dextro88
Harmless
*




Posts: 35
Registered: 20-10-2018
Member Is Offline


[*] posted on 15-1-2020 at 10:18


jealously i dont, but i dont find out why PPA dont work here ?
View user's profile View All Posts By User
karlos³
International Hazard
*****




Posts: 619
Registered: 10-1-2011
Location: yes!
Member Is Offline

Mood: verrückt & wissenschaftlich

[*] posted on 15-1-2020 at 11:49


Polyphosphoric acid is not a lewis acid.
View user's profile View All Posts By User
SWIM
International Hazard
*****




Posts: 657
Registered: 3-9-2017
Location: 26 Ancho street
Member Is Offline

Mood: when in danger or in doubt, run in circles, scream and shout.

[*] posted on 15-1-2020 at 12:21


There is an old JACS article (1940s? 1950s?) that covers the alkylation of aromatic rings with allyl chloride and Ferric chloride. I'll look for it.
Yields weren't great.

This was a method of making substituted amphetamines.
The reaction conditions also added hydrohalic acid across the double bond, so the result was actually the 2-chloro alkane, not the alkene.

This was directly converted to the amine by an SN2 reaction at high temperatures.

Not the same thing, but the closest thing I've heard of.

Could it work with allyl alcohol if you just threw more FeCl3 in there?
I'd guess maybe, but probably not very well, and the original reaction wasn't exactly high yielding anyway...

This process made 4-chloro, and 4-hydroxy amphetamines, but it wasn't tried with the more fragile methylenedioxy compounds.



[Edited on 15-1-2020 by SWIM]

edit: @Karlos: Yes, that is the paper I meant.
Thanks.

[Edited on 15-1-2020 by SWIM]




"You're not just telling us what we want to hear?"
"No Sir"
"Because we only want to hear the truth"
"Well, then I guess I am telling you what you want to hear."
"Son, didn't we just tell you not to do that?"

View user's profile View All Posts By User
karlos³
International Hazard
*****




Posts: 619
Registered: 10-1-2011
Location: yes!
Member Is Offline

Mood: verrückt & wissenschaftlich

[*] posted on 15-1-2020 at 12:40


You probably meant this paper, it is from 1946: https://chemistry.mdma.ch/hiveboard/rhodium/pdf/amination.ph...
There was a functioning clandestine lab found producing amphetamine with this method, somewhere in america, I don't know when but pretty early for clandestine amphetamine production.

[Edited on 15-1-2020 by karlos³]
View user's profile View All Posts By User
dextro88
Harmless
*




Posts: 35
Registered: 20-10-2018
Member Is Offline


[*] posted on 15-1-2020 at 12:49


Yes these can be used for drug cookery, but my goal is to succusfuly synthesis these md-ketones and add them to my colection of fragrances, so please any amphetamine synthesis discusion is out of question here, i have tried to prepare another ketones with FeCl3, but for aceptable yield i need to use 2-3x more of the aromatic hydracorbon, in this case its not practical for me to waste that much as solvent.

[Edited on 15-1-2020 by dextro88]
View user's profile View All Posts By User
karlos³
International Hazard
*****




Posts: 619
Registered: 10-1-2011
Location: yes!
Member Is Offline

Mood: verrückt & wissenschaftlich

[*] posted on 15-1-2020 at 13:52


Oh come on dextro I know you, if you want spoonfeeding at least tell the truth, no one will condemn you for it, unlike for lying just for your own benefit.
View user's profile View All Posts By User
Texium (zts16)
Administrator
********




Posts: 3158
Registered: 11-1-2014
Location: San Marcos, TX
Member Is Offline

Mood: Graduated

[*] posted on 15-1-2020 at 13:57


Honestly, it's painfully obvious... who goes out of their way to buy a kilo of a niche compound with an obvious, err, pharmacological connection for the sake of making a couple nice-smelling compounds?



Come check out the Official Sciencemadness Wiki
My YouTube Channel
My blog
(it doesn't like Chrome)
View user's profile Visit user's homepage View All Posts By User
dextro88
Harmless
*




Posts: 35
Registered: 20-10-2018
Member Is Offline


[*] posted on 15-1-2020 at 14:15


yes i agree it is,i bought a kilo because i knew it will dont happen at first trial and everythink is purely for my research purposes, but can we please continue discusing the main topic, im thinking to try the FeCl3 at equimolar ratio with the hydrocarbon and Nitromethane as solvent, and will report back in a few days :)

[Edited on 15-1-2020 by dextro88]
View user's profile View All Posts By User
karlos³
International Hazard
*****




Posts: 619
Registered: 10-1-2011
Location: yes!
Member Is Offline

Mood: verrückt & wissenschaftlich

[*] posted on 15-1-2020 at 14:20


I used nitromethane as solvent for FC alkylations very well.
But you need another lewis acid for this to work, something that does not give off HCl.
View user's profile View All Posts By User
dextro88
Harmless
*




Posts: 35
Registered: 20-10-2018
Member Is Offline


[*] posted on 15-1-2020 at 14:25


why whats the problem with hcl evolution, the only catalyst that i know for this reaction that did not produce hcl vapours is PPA and it seems to do not work, i might try again maybe the problem was in me, since i have some suspision the condenser wasnt absolutly dry.

[Edited on 15-1-2020 by dextro88]
View user's profile View All Posts By User
karlos³
International Hazard
*****




Posts: 619
Registered: 10-1-2011
Location: yes!
Member Is Offline

Mood: verrückt & wissenschaftlich

[*] posted on 15-1-2020 at 15:13


It does not work because it is not a lewis acid.
You need a lewis acid, and what do you think is the issue with AlCl3? It is the HCl it produces of course.
If you want to make something from that stuff, why not directly going via FC acylation instead of alkylation?
At least that would work with PPA.
View user's profile View All Posts By User
clearly_not_atara
International Hazard
*****




Posts: 1797
Registered: 3-11-2013
Member Is Offline

Mood: Big

[*] posted on 15-1-2020 at 17:30


Even if this reaction worked, you would get 6-methylsafrole, or respectively 6-methyl-3,4-methylenedioxypropiophenone, not the isomer you want. The starting material you need is 2,3-methylenedioxytoluene.



[Edited on 04-20-1969 by clearly_not_atara]
View user's profile View All Posts By User
dextro88
Harmless
*




Posts: 35
Registered: 20-10-2018
Member Is Offline


[*] posted on 16-1-2020 at 03:59


can you draw please what you mean by 6methylsafrole ? Another route i am thinking is bromination of hydrocarbon and go grignard to 5M-Safrole with allyl chloride and phenylmagesium.
View user's profile View All Posts By User
Corrosive Joeseph
International Hazard
*****




Posts: 735
Registered: 17-5-2015
Location: The References Forum
Member Is Offline

Mood: Cyclic

[*] posted on 16-1-2020 at 07:45


Quote: Originally posted by dextro88  
can you draw please what you mean by 6methylsafrole ?


How hard is that......? The chain is number one carbon on the ring, so count around to number 6...... And it happens to be the one next to it.

Here is the corresponding amphetamine - https://en.wikipedia.org/wiki/6-Methyl-MDA


/CJ




MSDS Addict and OTC Slut
View user's profile View All Posts By User
dextro88
Harmless
*




Posts: 35
Registered: 20-10-2018
Member Is Offline


[*] posted on 16-1-2020 at 09:09


what product will give the grignard then ? Im looking for possible 5-Methyl or 2-Methyl substition.
View user's profile View All Posts By User
Abromination
National Hazard
****




Posts: 411
Registered: 10-7-2018
Location: Alaska
Member Is Offline

Mood: Fumehood building!

[*] posted on 16-1-2020 at 15:52


Why are we answering this blatant spoonfeeding request?



List of materials made by ScienceMadness.org users:
https://docs.google.com/spreadsheets/d/1nmJ8uq-h4IkXPxD5svnT...
--------------------------------
Elements Collected: H, Li, B, C, N, O, Mg, Al, Si, P, S, Fe, Ni, Cu, Zn, Ag, I, Au, Pb, Bi, Am
Last Acquired: B
Next: Na
--------------
View user's profile Visit user's homepage View All Posts By User
j_sum1
Administrator
********




Posts: 5137
Registered: 4-10-2014
Location: Oz
Member Is Offline

Mood: Metastable, and that's good enough.

[*] posted on 16-1-2020 at 16:36


Quote: Originally posted by Abromination  
Why are we answering this blatant spoonfeeding request?

Good point. I let it by initially since it was an explicit question about catalysis of a process.

Now I think it has run its course. We are talking a commercial operation with kilogram quantities of reagents. The interest is only in the product and not the chemistry. And the subject of questions has traversed from catalysts to the difference between alcohols and carboxylic acids, then on to the topic of lewis acids, then nomenclature and now on to Grignards. All in 20 short posts.

@dextro88, this is a chemistry hobby forum not a repository for drug synthesis procedures. Stick around for the chemistry if you want to. But no one is going to be propping up your little clan lab operation.

Any questions, U2U.
View user's profile View All Posts By User
j_sum1
Administrator
Thread Moved
16-1-2020 at 16:36

  Go To Top