Author Topic: 1-Phenyl-2-Propanone synthesis Overview.  (Read 2142 times)

Sedit

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #40 on: July 04, 2009, 08:07:35 AM »
kiddin me Iv been perscrived to them for a while... yeh im a bit out of it but after 6 six pack and 3 xanax most peoples would be sllepping by now.

The yeilds are fine frm what I hear. I think Noino should get some ammerican freinds that are higher up and they may be able to show him first hand how to fix his yeilds. since hes working with NaOH I fear hes trying the aldol but base catylized. I sure hope not because in this case the product is completely diff
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2bfrank

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #41 on: July 04, 2009, 08:59:27 AM »
check your messenges (pm) that is.

2b
« Last Edit: July 04, 2009, 09:07:07 AM by 2bfrank »

Amphetamine Chemist

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #42 on: August 11, 2009, 09:43:56 AM »
Quote
Must be because you sure as fuck can't stop the drugs, they will come from other places. You can't stop the real chemist because carbon has to many uses.

Dead right my man. They can't stop us, many of the chemicals used to make P2P are impossible to ban, as they are everywhere, acetone for instance, benzene for instance, impossible, benzene is too easy to make, plus Sodium Benzoate is cheaper than sand almost.

Speaking of which, the easiest way to make P2P is by far the benzene/chloroacetone synth, honestly, from an economical perspective, you can't go past it. I Myself am in the process of trying to make P2P this way, i have chloroacetone, and benzene, all i need now is anhydrous aluminum chloride and i will begin the synth, something that worries me however is the purity of the chloroacetone i have made. May i start a thread on all of the precursors for this friedel-crafts reaction? That way it can be organized easily.

Not to mention once you have P2P, you can react it with a bunch of things to make all sorts of phenethylamine analogs more or less. Not just meth or amphetamine, as has been said.

Thanks.
- AmphChem.

java

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #43 on: August 11, 2009, 01:14:18 PM »
Synthesis of Arylpropylamines. I. From Allyl Chloride
T. M. Patrick Jr., E. T. McBee, H. B. Hass
J. Am. Chem. Soc. 1946, 68 (6), pp 1009–1011




Summary
The reaction of allyl chloride and benzene in the presence of ferric chloride to produce 2-cllloro-1- phenylpropane, described by Nenitzescu and
Isacescu, has been extended to four other aromatic compounds. Total yields of arylchloropropanes were 14 to 53%.
Truff ault's method of adding aromatic compounds to allyl chloride in the presence of sulfuric acid was utilized for the preparation of 2-aryl-lchloropropanes.
Nine arylchloropropanes have been treated with alcoholic ammonia to give 20-51% yields of the corresponding arylpropylamines. Five of the
arylchloropropanes yielded 24432% of the Nmethylarylpropylamines
on treatment with alcoholic methylamine.

 



Note: ....from (available at gigapedia.com) page 119,

 Synthesis of Essential Drugs
 R.S. Vardanyan and V.J. Hruby[/
 ISBN: 978-0-444-52166-8

http://ifile.it/4orp9lk/dkzpq.rar 










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Amphetamine Chemist

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #44 on: August 11, 2009, 01:52:56 PM »
Thanks but why not just make d-amphetamine by reacting P2P with 25% Ammonia, instead of methylamine, and then splitting the racemic amph into the 2 isomers with d-tartric acid as the article you posted mentioned?? D-Amphetamine is much better than L-amphetamine, i love the stuff.  ;) Obviously.

Thanks.
- AmphChem.

heisenberg

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #45 on: August 11, 2009, 07:17:20 PM »
Thanks but why not just make d-amphetamine by reacting P2P with 25% Ammonia, instead of methylamine, and then splitting the racemic amph into the 2 isomers with d-tartric acid as the article you posted mentioned?? D-Amphetamine is much better than L-amphetamine, i love the stuff.  ;) Obviously.

A reductive amination of P2P with methylamine yields racematic methamphetamine, not amphetamine. Amphetamine could be made from P2P by reacting it with hydroxylamine, and then reducing the oxime.
I spent all my money on booze and hookers, the rest I wasted - Charles Bukowski

Sedit

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #46 on: August 11, 2009, 07:25:10 PM »
This is more of an overview threed Amphetamine chemist, Methods of synthesis are well known and spread far and wide on the internet. With little need to rehash old discussion. What java preposes is a method that is quite different the the means that have been discussed to death with still little experimental data compared to the amount of talk of various methods.


But with that all said  am all for the discussion of new and promising ways to get from point A to point B
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Amphetamine Chemist

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #47 on: August 12, 2009, 03:52:14 AM »
I Understand. My philosophy however is more streamlined, if i where to make unmethylated amphetamine i would simply react P2P with ammonia gas under high pressure with a nickel catalyst. As is well known like you said thereinof, but easier.  :D

But now since i understand that this thread is for novel and improvised ways to make such compounds, i will leave it at that.

Thanks.
- AmphChem.

Sedit

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #48 on: August 12, 2009, 01:56:28 PM »
Synthesis of Arylpropylamines. I. From Allyl Chloride
T. M. Patrick Jr., E. T. McBee, H. B. Hass
J. Am. Chem. Soc. 1946, 68 (6), pp 1009–1011




Summary
The reaction of allyl chloride and benzene in the presence of ferric chloride to produce 2-cllloro-1- phenylpropane, described by Nenitzescu and
Isacescu, has been extended to four other aromatic compounds. Total yields of arylchloropropanes were 14 to 53%.
Truff ault's method of adding aromatic compounds to allyl chloride in the presence of sulfuric acid was utilized for the preparation of 2-aryl-lchloropropanes.
Nine arylchloropropanes have been treated with alcoholic ammonia to give 20-51% yields of the corresponding arylpropylamines. Five of the
arylchloropropanes yielded 24432% of the Nmethylarylpropylamines
on treatment with alcoholic methylamine.

After reading thru the paper I must say this is a pretty elegant reaction. The yeilds are on the low side ranging about 30% give or take for the substrate most would desire but its pretty interesting that the reaction proceeds thru the interemediat allylbenzene which is clorinated thru the use of the formed HCl from the degregation of the FeCl3. I wounder what could be done to increase the yeilds on this reaction. I didn't see any mention of recovery of unreacted allylbenzene but I may have missed it.


Im going to see if I can track down the original text by Nenitzescu and Isacescu and see what they have to say about this reaction.
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POSEIDON

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #49 on: August 14, 2009, 03:53:49 AM »
sedit i think this is the patent you looking for:
http://www.freepatentsonline.com/3678122.html
The chemists are a strange class of mortals, impelled by an almost insane impulse to seek their pleasures amid smoke and vapour, soot and flame, poisons and poverty; yet among all these evils I seem to live so sweetly that may I die if I were to change places with the Persian king.
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Sedit

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #50 on: August 14, 2009, 04:45:08 AM »
Thank you POSEiDON I dont know if thats the text from Nenitzescu referenced in the paper Java uploaded but it still looks useful non the lest.

Amphetamine chemist you spoke of using NH3 to form amphetamine, can you explain the mechanism thru which this forms? Why do people always use hydroxyl amine to form amphetamine if NH3 would work?

Bear with me here people.
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heisenberg

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #51 on: August 14, 2009, 05:30:32 AM »
@Sedit

I think that this is what he's talking about. I'm assuming that he meant Raney nickel...

Quote
High Pressure Reductive Amination of 1-Phenyl-2-Propanone Utilizing Raney Nickel:

Organicum: Practical Handbook of Organic Chemistry (Addison-Wesley Publishing Co., Inc., 1973), English translation by B. J. Hazzard, 458-9 and 686.

In working with Raney nickel, Hazzard states that a highly basic catalyst (e.g., that of Urushibara prepared from 30% nickel alloy, see catalyst preparation below) gives the best results.

134.2 g. (1.0 mole) of phenyl-2-propanone is dissolved in 500 ml of methanol that has been saturated with ammonia at 10C (about 94 g. or 5.5 moles). After the addition of Raney nickel from 30 g. of alloy, hydrogenation is carried out in a shaking or stirring autoclave at 90C and 100 atm. After the uptake of hydrogen has ceased, the pressure is released, the catalyst is filtered off, and the solvent is distilled off. The residue is acidified with 20% hydrochloric acid to Congo Red (i.e., to pH 3; Congo Red is blue- violet at pH 3.0 and red at pH 5.0) and the non-basic impurities are extracted with ether. The ethereal extract is discarded and, with efficient cooling, the aqueous solution is made alkaline with 40% sodium hydroxide solution and is repeatedly extracted with ether. The extract is dried over potassium hydroxide. After the solvent has been evaporated off, the product is distilled through a 20-cm Vigreux column to obtain a 90% yield of DL-1-phenyl-2- aminopropane, b.p. 12mm. 92C.
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RoidRage

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #52 on: April 26, 2011, 06:07:39 AM »
Ahh...I hate myself a bit for bumping such a old (but really interesting thread), but anyway, it seems to be the norm here rather than starting a new thread. Anyway, the thread died unexpectably and I'm sure plenty more infos will be posted ;D

I'm interested in getting the obviously missing reaction diagram in the original post. I suppose the picture was linked externally so that's why it's now unavailable.

Thanks

Vesp

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #53 on: April 26, 2011, 07:20:31 AM »
Good news for you - I took the time to upload the picture again... it was originally located on the FTP and I have now attached it to the post...


Also - its good to bring up old posts vs start new of the same. Feel free to bring back all of the "dead" posts, as many as you like haha
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RoidRage

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #54 on: April 26, 2011, 07:29:15 AM »
Good news for you - I took the time to upload the picture again... it was originally located on the FTP and I have now attached it to the post...


Also - its good to bring up old posts vs start new of the same. Feel free to bring back all of the "dead" posts, as many as you like haha



Hell yeah, thanks Vesp!

As for bumping old threads, my logic was correct then ;) It's the kind of practice strongly discouraged in ''mainstream'' forums, but this forum is far from that haha :D ;D Can excellent, thoughful information ever gets old anyway  ;)?

Vesp

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #55 on: April 26, 2011, 07:40:06 AM »
Most forums exist to make money off of adds or to get more hits than the day before for one reason or another. That is why they want new threads since that => more pages, more views, same info in different words so they still get "original" content to get a higher ranking...

ha anyways i'll leave this thread be and go where it should instead of derailing it - as I have nothing to contribute other than that picture. Just wanted to make it clear that posting in old threads is a good thing.
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beanhead

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #56 on: April 26, 2011, 11:26:30 AM »
Thanks but why not just make d-amphetamine by reacting P2P with 25% Ammonia, instead of methylamine, and then splitting the racemic amph into the 2 isomers with d-tartric acid as the article you posted mentioned?? D-Amphetamine is much better than L-amphetamine, i love the stuff.  ;) Obviously.

Thanks.
- AmphChem.

If you went from Phenyl-2-nitropropene you can go to amphetamine, as stated above P2P forms methamphetamine.

Phenylacetone + NH3 does in fact work but yields are low, it's fun for MDA facture though. I think it itsn't used much sedit because it's a weak nucleophile. Don't forget about our precious Leuckart though ! You could use formaldehyde along with ammonium chloride to get to P2NP.

If you have benzaldehyde and want to refrain using nitroethane why not go with the crossed aldol between benzaldehyde and MEK with HCl gas (methyl phenyl butanone), followed by a Baeyer-Villiger to give the P2P enol ester, which then is saponified with diluted NaOH.

Yields are not that promising (35% from methyl phenyl butanone) but everything used but the benzaldehyde is available in the hardware store.


German vespiates(?) if you'd like to translate this, always welcome   :P

If you hydrolyze Sodium Cyclamate artificial sweetener, you get cyclohexylamine, and a lot of it.


Balkan Bonehead

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #57 on: April 29, 2011, 12:29:40 AM »
Chlorination and hydrolysis of styrene.

Also, I have been looking into the Meerwein arylation of aniline with methyl methacrylate. This will yield 2-chloro-2-carbomethoxy-phenylpropane. Ammonolysis gives a-methylphenylalanine, while elimination w/ aqueous alkali gives beta-methylcinnamic acid. Hypochlorination followed by epoxidation leads (I think) to halodecarboxylation and rearrangement to the ketone (p2p) on acid treatment. I believe this leads to the same intermediary as Darzen's condensation with chloropropionate and benzaldehyde.

Methyl methacrylate can of course be had by depolymerizing acrylate plastics, and the Meerwein arylation is really simple. It's even done as an undergraduate lab (cinnamic acid from acrylate). http://pubs.acs.org/doi/abs/10.1021/ja01241a019

Regards.

Balkan Bonehead

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #58 on: April 29, 2011, 04:09:33 AM »
The little birdy says that anhydrous sodium acetate will work in place of lead acetate in the destructive distillation tek in comparable yield, so long as a 2:1 molar ratio of sodium acetate:ferrous sulfate catalyst is added and intimately mixed.

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #59 on: November 05, 2012, 08:29:17 PM »
I don't believe benzene to be over the counter sinces its been baned or its use in almost anything.

Many single electron oxidising agents work for this synthesis but Mn(III) has the best results from the documentation I have read. When dealing with MD derivitives theres no garentee that it will add para to the methylenedioxy bridge and some cases it may add ortha/meta leading to other compounds and where as there known to be active(more so IIRC) there not the substance one would think there ingesting.

If someone wanted to make Phenyl Propanone from acetone and benzene there best bet for a smooth reaction would be to chlorinate the Benzene or Methylenedioxy benzene and then expose to acetone to an extreamly strong base such as sodamide or tert-potassium- butoxide to form the acetone enolate and directly condense the two in 76% yeilds IIRC.

As a stand by with the chloro benzene Friedel-Crafts alkylation  with AlCl3 and acetone or benzene and chloro acetone.

I've heard the Mn(III)AcO synth hasn't been at all successful on more than one occasion and in each situation only dry lab grade reagents were used. I'm not sure why but one theory is that the Mn(IV) salt may have form Mn(II) during or prior to its conversion to Mn(III)AcO. Another being the oxidation method to go from the (II) to the (III) state, CaOCl2 was used in each report rather than the other electro/chemo methods. Any thought you guys have would bee most welcome.

I like the sound of the chlorobenzene aceton enolate method though, aremthere any available refs for it?