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

Quantum Dude

  • Subordinate Wasp
  • ***
  • Posts: 192
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #20 on: June 02, 2009, 10:34:41 PM »
Im suprised that no one is discussing the conversion of cinnamaldehyde to P2P using the Huang Minlon elimination followed by standard peroxidation of propenylbenzene to P2P. I would love to hear reports on this.



Sedit

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 2,099
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #21 on: June 03, 2009, 12:44:45 AM »
Yes indeed, I have heard mention and experimental data from some people that performed this first hand also. The fisrt step of the synthesis anyway, after that they opted to form the chlorohydrine and expoxidate that.

Lets not forget the other valuable aspect that cinnamaldehyde has in that it can be converted to Benzaldahyde in good yeilds by refluxing it with sodium carbonate. Which ever means suites ones materials and experiances makes cinnamaldehyde a good buy even if its price is a bit higher then many other essential oils.
There once were some bees and you took all there stuff!
You pissed off the wasp now enough is enough!!!

timecube

  • Subordinate Wasp
  • ***
  • Posts: 230
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #22 on: June 03, 2009, 10:24:09 PM »
Quote
There are so many means to an end I fail to understand why majority of people take the most complicated, time consuming, and expensive means of all by extracting 20 boxes of pills and then hunting for Iodine, and scraping the backs of sometimes over 10,000 books of matchs to yeild maybe an ounce of product.

Reducing (pseudo)ephedrine does give enantiomerically pure product.

I think the labor intensive methods caught on mainly because they didn't require any real talent for chemistry, and since the users were going to be up all night anyway, they'd might as well scrape some match books.

A lot of chemists seem to write off MA syntheses as not worth exploring since someone with no talent can in theory arrive at the same end product, but there are plenty of interesting pathways worth exploring and many of the processes should apply equally well to MDMA synthesis.. (MD)phenylacetic acid, (MD)benzaldehyde, etc..

Sedit

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 2,099
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #23 on: June 04, 2009, 03:52:39 AM »
Sorry I have not been able to really follow up with other methods because Iv been two busy to post anything indepth latly.(Didnt have time to write the first post the way I wanted to). But I assure you there are many more to come time permitting.


Quote
A lot of chemists seem to write off MA syntheses as not worth exploring since someone with no talent can in theory arrive at the same end product, but there are plenty of interesting pathways worth exploring and many of the processes should apply equally well to MDMA synthesis.. (MD)phenylacetic acid, (MD)benzaldehyde, etc..

Exactly, Thats one of the main reasons I started this topic. Not so much a how to meth tech but there are so many possible synthesis it can be more of a organic advanced drug chem 101 so to speak. Its a simple enough substance that total synthesis is within reach of anyone with the determination to acheive it and in the process of showing different pathways much more information can be gathered for other synthesis such as how to condense materials with aldahydes, how to chlorinate alkanes, how to turn a chlorinated alkane into an aldahyde ect..ect.. you get the point. Its a great brain exercise to keep ones organic chemistry skills in tip top shape and maybe learn a thing or two.
There once were some bees and you took all there stuff!
You pissed off the wasp now enough is enough!!!

2bfrank

  • Guest
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #24 on: June 04, 2009, 11:37:06 AM »
I thought Hex was talking about a nitroethene, which I thought could of been of interest, if the prep was easy etc, and then this reduced. I have also thought of preparing 2-nitroethanol, and adding sodium bisulfate to remove the OH and create unsaturation, that then could be reduced. I need to think about this more, and be dam careful about playing around with lower alkane nitro compounds. I may well buy some silver and make the silver nitrite and do that prep. It is the challenge that is of interest. but yields help.

2bfrank

  • Guest
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #25 on: June 04, 2009, 12:19:26 PM »
1-Phenyl-2-Propanone synthesis.

Reaction of Acetone and benzene, and the inclusion of Manganese(111)acetate as catalyst.
Yields arent great aprox 36%, but with cheap solvent and cheap(OTC) reagants fullstop, this appears to be worthy of another mention.

« Last Edit: June 07, 2009, 07:16:41 AM by Vesp »

timecube

  • Subordinate Wasp
  • ***
  • Posts: 230
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #26 on: June 04, 2009, 02:39:18 PM »
Quote
Reaction of Acetone and benzene, and the inclusion of Manganese(111)acetate as catalyst.

I actually hadn't seen this before, but this seems extremely straightforward.  I believe it could add properly to (MD)benzene too.

http://www.erowid.org/archive/rhodium/chemistry/manganous.acetate.html

Sedit

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 2,099
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #27 on: June 04, 2009, 02:53:41 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.
There once were some bees and you took all there stuff!
You pissed off the wasp now enough is enough!!!

timecube

  • Subordinate Wasp
  • ***
  • Posts: 230
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #28 on: June 05, 2009, 08:38:24 AM »
Benzene isn't OTC (though you can find it online sometimes) but can be produced from sodium benzoate and likely a few other methods.

video demo:  hxxp://www.youtube.com/watch?v=sYyw_hrXrZ8


I know brominating (md)benzene tends to mostly add in the para position where you want it, which is why I believe this might add properly.  (I'll try to find some references.  I've never seen any directly pertaining to producing 1,2md-4-bromobenzene other than as an intermediary to other products, but it seems to work about the same way as producing bromobenzene.)

I have given some thought before to the enolate method.  Here are a couple versions of an org. chem. class lab procedure demonstrating aldol condensation using NaOH to form the enolate rather than stronger bases that require more preparation.

hxxp://www2.volstate.edu/chem/2020/Labs/Aldol_Condensation.html
hxxp://www.chm.davidson.edu/erstevens/381aldol.pdf

I do not know if polymers would try to form with P2P and bromobenzene although it seems fairly likely and has been my main concern with the enolate method.  Unfortunately, I don't currently have lab access to try it.
« Last Edit: June 05, 2009, 08:45:41 AM by timecube »

2bfrank

  • Guest
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #29 on: June 22, 2009, 10:54:18 PM »
my bad, benzene is not so OTC. A friend deals with an industrial supply - cleaning co, and they can order it, so perhaps it is obtainable. Be careful of middleman though, Who knows who they are shaking hands with. Cash sales for starters are perhaps a light.

Goldmember

  • Subordinate Wasp
  • ***
  • Posts: 132
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #30 on: June 26, 2009, 07:49:59 AM »
Reaction of Acetone and benzene, and the inclusion of Manganese(111)acetate as catalyst.
Yields arent great aprox 36%, but with cheap solvent and cheap(OTC) reagants fullstop, this appears to be worthy of another mention.

Figure how much manganese acetate is needed and the it becomes ugly.

Vesp

  • Administrator
  • Foundress Queen
  • *****
  • Posts: 3,130
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #31 on: June 26, 2009, 07:56:10 AM »
Even if it uses a lot of manganese acetate, isn't that easy to make and recycle?
Bitcoin address: 1FVrHdXJBr6Z9uhtiQKy4g7c7yHtGKjyLy

magnificent bastard

  • Larvae
  • *
  • Posts: 2
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #32 on: June 29, 2009, 01:25:12 AM »
I've seen nitroethane synth, how bout something like nitromethane

Sedit

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 2,099
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #33 on: June 29, 2009, 01:28:33 AM »
What?
There once were some bees and you took all there stuff!
You pissed off the wasp now enough is enough!!!

Vesp

  • Administrator
  • Foundress Queen
  • *****
  • Posts: 3,130
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #34 on: June 29, 2009, 01:34:56 AM »
Off topic much? Perhaps you meant to post this in the nitroethane section?
Bitcoin address: 1FVrHdXJBr6Z9uhtiQKy4g7c7yHtGKjyLy

Douchermann

  • Dominant Queen
  • ****
  • Posts: 397
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #35 on: June 29, 2009, 06:55:21 PM »
Perhaps he's talking about the nitrostyrene from benzaldehyde, as opposed to the nitropropane from benzaldehyde.  The nitrostyrene will just produce phenethylamine upon reduction.  However, many substituted benzaldehydes will produce pharmacologically active substances upon producing the subst. phenethylamine.

2bfrank

  • Guest
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #36 on: July 02, 2009, 05:23:15 AM »
They stoped MDMA by making it cost to much to make.... now they bitch about the meth problem.... Let them make E and you wont have as big a meth problem.
They don't want to win - just to play.

I think this shows the correct product of BzO + MEK:
[/quote

Any refs for that procedure..... purely for academic reasons

2b
« Last Edit: July 02, 2009, 05:25:10 AM by 2bfrank »

2bfrank

  • Guest
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #37 on: July 03, 2009, 07:58:49 AM »
Sedit,

been discussing the HCl catalysed prep of benzaldehyde with MEK
So far Noino(my eastern friend) has found the following.
The first part of this overall reaction between benzaldehyde and MEK with the Hydrogen chloride(anhydrous) as catalast gives the compound of 3-methyl-4-phenyl-3-buten-2-one, and is discussed in the following article.

Martin Stiles, Daniel Wolf, Gwyn V. Hudson
J. Am. Chem. Soc., 1959, 81 (3), pp 628–632

The reaction between 3-methyl-4-phenyl-3-buten-2-one is then discussed further, but in a different context, a context that is not backed up with Sc literature. So far, it is

1)An acid catalysed Aldol condensation of Benzaldehyde and Methyl Ethyl Ketone to give a Methyl Phenyl Butenone ie C6H5CHO + CH3CH2COCH3 + dryHCL ---> C6H5CH=C(COCH3)CH3 or 3-methyl-4-phenyl-3-buten-2-one

2) The unsaturated ketone undergoes the Baeyer-Villiger oxidation with peroxy acids to give the enol ester of Phenyl propanone ie C6H5CH=C(COCH3)CH3 + RCO3H ----> C6H5CH=C(OCOCH3)CH3

3) The enol ester is then saponified with 10% NaOH solution to give Phenyl Propanone in about 35% yield based on the unsaturated ketone. Obviously this could be the stated acid based hydrolysis giving the same product. Noino was thinking of looking into this some more. Perhaps has got this all wrong, any help, or an even more accurate understanding of this possible procedure would be good. Perhaps what has been detailed by my friend is all wrong,

2b

Sedit

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 2,099
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #38 on: July 04, 2009, 02:52:08 AM »
Sorry about the delay. I feel like I gave birth to this threed just to get charged with child abandonment.
My minds been really wraped up in other reactions and personal shit lately.

However, you will not find much literature in forums on this other then a few threeds here and there unless you dig thru carefully because those who know ain't talking much and for good reason. Its an acid cataylised aldol condensation between BnO and MEK. This can be reversiblely hydrolysised to Hydroxyl Methyl Phenyl Butanone so anhydrous conditions are absolutly needed. (anhy)HCl has had the best first hand yeilds from what I have heard here and there but Concentrated H2SO4 can also be used. Also it can more then likely be performed under the influence of a strong Lewis acid + H2O2 combination.

The formed MePhBuO is oxidised to the intermediat Phenyl-propenyl-acetate which further reacts in the (aq)acidic enviroment hydrolysis to yeild Phenyl-2-Propanone. This is has been reported although not in forums that I am aware of to be highly exothermic so care must be taken to slowly care for the reaction speed.

My honestly belief is that of most others that have heard of this reaction chose not to make it a wide spread idea and thats that best case because all it takes is one lab to go down thru this process and all the sudden you get funny looks trying to buy the materials and after that there completely off the shelfs. Best bet is to understand the reactions, read up, and communicate everything first hand via PM. I do alot of restoration work on old furniture and would hate to see my favorite MEK paint strippers go the way of the doe-doe. Its already bad enough I can't bake my favorite cherry candys without looking suspicious I would hate to lose the other half of the hobby.

Saponification with NaOH is not needed as far as I know and on the previous page delic posted a reaction schematics of the reaction the hydrolysis is handled thru the acid. Look over at SciMad for some decent threeds on this topic also.

Now if you don't mind Sedits going to indulge in some malt EtOH and Benzodiazepines so for the rest of the night take his word with a grain of salt. ;D HAPPY freedom day in 30 mins every one.
« Last Edit: July 04, 2009, 05:59:59 AM by sedit »
There once were some bees and you took all there stuff!
You pissed off the wasp now enough is enough!!!

2bfrank

  • Guest
Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #39 on: July 04, 2009, 06:33:58 AM »
Yes, I understand,
My Japanese Chemist friend Noino, pm'd me yesterday in fact and stated quite categorically that the reaction is extremely difficult to perform. Requires "plenty experience" and very good equipment, and even then yields are inconsistent and dismal. Doesn;t sound like much chop, but what is of interest is a range of condensations that could produce heaps of possibilities where one could explore lots of reactions and do so legally. Sort of like kicking a football around, but in this case, perhaps a benzylic alcohol.

ps, hope your evening was fun, pity you probably cannot remember much of it,, But you know what they say about memories though, well hang on, Ill get back to you on that one...........