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

coincoin

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #60 on: December 23, 2012, 07:22:29 AM »
Zinc powder has been shown to be an effective friedel craft activator instead of anhydrous AlCL3. And this with or without microwave irradiation

Zinc Mediated Friedel–Crafts Acylation in Solvent-Free Conditions under
Microwave Irradiation (see ref section i think)

fishinabottle

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #61 on: December 24, 2012, 07:47:47 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.

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.

Well Rayney Nickel and alcoholic amonia gives up to 95% - at 100atm pressure. Neither the catalyst nor the apparatus (also labgrade hydrogen gas is needed) are in reach for the very most.

The hydroxylamine (easily made from nitromethane btw.) is the preferred way to go and if one adds 25% ammonia solution to the mix it gives excellent yields too.

/ORG

Wizard X

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #62 on: December 24, 2012, 11:37:41 PM »
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.

Well Raney Nickel and alcoholic ammonia gives up to 95% - at 100atm pressure. Neither the catalyst nor the apparatus (also lab-grade hydrogen gas is needed) are in reach for the very most.

The hydroxylamine (easily made from nitromethane btw.) is the preferred way to go and if one adds 25% ammonia solution to the mix it gives excellent yields too.

/ORG


Low Pressure Reductive Amination of 1-Phenyl-2-Propanone Utilizing Raney Nickel: http://www.erowid.org/archive/rhodium/chemistry/reductive.amination.html

Haskelberg, Aminative Reduction of Ketones. J. Am. Chem. Soc., 70 (1948) 2811-2; C.A. 43: 1349f (1949).

Phenylacetone (1-phenyl-2-propanone) was catalytically converted to beta-phenylisopropylamine (amphetamine) using ethanolic ammonia, hydrogen at about atmospheric pressure and Raney Nickel. A yield of 85% was obtained.
Albert Einstein - "Great ideas often receive violent opposition from mediocre minds."

fishinabottle

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #63 on: December 25, 2012, 08:58:14 AM »
Well there seems to have been a dent in the probability distribution of spacetime at about 1948 somewhere in the USA, making certain chemicalreactions run different. Just what happens in quantum mechanics  ;D

After my best of knowledge nobody has been able to repeat this, not with normal Rayney Nickel at least (W6-7 is something else, but we know those are out of reach for us).
Anybody working with Rayney Nickel as we know it and in special those writing books (like the ORGANIKUM, but what do they know?) seemed to have been committed to explicitely proclaim that with less then 50atms you are pretty fucked in making Amphetamine by P2P-ammonia-Rayney.

But I don't give a fuck, who wants may follow your suggestion and pay the price. Will not be the first ones  :P


regards
/ORG

Wizard X

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #64 on: December 26, 2012, 12:47:32 AM »
Well there seems to have been a dent in the probability distribution of spacetime at about 1948 somewhere in the USA, making certain chemicalreactions run different. Just what happens in quantum mechanics  ;D

After my best of knowledge nobody has been able to repeat this, not with normal Rayney Nickel at least (W6-7 is something else, but we know those are out of reach for us).
Anybody working with Rayney Nickel as we know it and in special those writing books (like the ORGANIKUM, but what do they know?) seemed to have been committed to explicitely proclaim that with less then 50atms you are pretty fucked in making Amphetamine by P2P-ammonia-Rayney.

But I don't give a fuck, who wants may follow your suggestion and pay the price. Will not be the first ones  :P


regards
/ORG

Reaction conditions vary greatly when using  Raney Nickel. In the simplest terms, when hydrogen is absorbed (pressure decrease) and when the absorption ceases, you know catalytic hydrogenation has occurred.



Evolution of Titanium(IV) Alkoxides and Raney Nickel for Asymmetric Reductive Amination of Prochiral Aliphatic Ketones. http://pubs.acs.org/doi/abs/10.1021/ol051909v

The Preparation of Raney Nickel Catalysts and their Use Under Conditions Comparable with Those for Platinum and Palladium Catalysts. (1948) http://pubs.acs.org/doi/abs/10.1021/ja01182a080

CATALYST, RANEY NICKEL, W-6 (Adkins and Billica, J. Am. Chem. Soc., 70, 695 (1948). http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv3p0176

CATALYST, RANEY NICKEL, W-2. http://www.orgsyn.org/orgsyn/prep.asp?prep=CV3P0181


To a solution of 41.6 g. (0.25 mole) of purified 2,3-dimethoxybenzaldehyde (Note 1) in 150 ml. of 95% ethanol is added 23.4 g. (0.75 mole) of methylamine in 50 to 75 ml. of water (Note 2). The mixture is heated to boiling and placed in a 500-ml. heavywalled bottle (Note 3), and 6 g. of Raney nickel catalyst is added (Note 4). The bottle is connected to a low-pressure hydrogenation apparatus,2 the system is flushed with hydrogen, and the mixture is shaken with hydrogen at an initial pressure of 45 lb. until 0.25 mole of hydrogen is absorbed and the absorption ceases (Note 5).

(Note 5) The time required depends upon the activity of the catalyst and the temperature of reaction. The submitters reported that 90–95% of the calculated amount of hydrogen was taken up in 90 minutes at 70° whereas 20 hours was required at room temperature. The checkers found the reaction to be complete after 36 to 41 minutes, the temperature dropping during the period from 70° to 30° since no provision was made for heating. When the whole hydrogenation was carried out at room temperature the period of reaction was 90 minutes with the W-6 Raney nickel catalyst. http://www.orgsyn.org/orgsyn/prep.asp?prep=CV4P0603



a-Phenylethylamine has been prepared by reducing acetophenone with hydrogen at high pressures (3500-5000 PSI) over nickel catalysts in the presence of liquid ammonia; [1,2]

...with hydrogen at low pressures over a nickel catalyst in the presence of ammonia-saturated ethanol;[3]

http://www.orgsyn.org/orgsyn/prep.asp?prep=CV3P0717


« Last Edit: December 26, 2012, 10:09:47 PM by Wizard X »
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Doc B

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #65 on: February 10, 2013, 12:29:28 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.

Sedit, did you (or has anyone else) have the Nenitzescu and Isacescu text?

I didn't notice any mention in the linked text of recovered allybenzene either. Yet I am aware of allylbenzenes being recoverable byproducts in amoniolysis of arylbromopropanes. Given the linked text does mention the more liable halogens giving lower yields and the lists other byproducts formed, at least to some extent, I'm thinking none are formed via the arylchloro route. Anyone's thoughts or experience on the FC alk's &/or halogenation of aromatic allyls with different halides would be most helpful in gaining a comparative understanding and useful strategies in both optimisation of procedure, yield, and recovery of useful byproducts.

coincoin

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #66 on: February 17, 2013, 11:02:34 AM »
guess no one read my previous post...

fishinabottle

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #67 on: February 17, 2013, 03:44:45 PM »
guess no one read my previous post...
Why do you think so? It was not really groundbreaking. The article is known and IIRC the method is volumetrically unfavorable and I am not sure if it can be reproduced at all not to talk about if with the yields.
If you have some ideas, references whatever to make this more attractive pls tell, I at least am eager to hear about it.
Would be kind though if you could provide links instead of "is somewhere..." Would be helpful too, really.

regards
/ORG

lugh

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #68 on: February 17, 2013, 05:57:43 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.

Sedit, did you (or has anyone else) have the Nenitzescu and Isacescu text?

I didn't notice any mention in the linked text of recovered allybenzene either. Yet I am aware of allylbenzenes being recoverable byproducts in amoniolysis of arylbromopropanes. Given the linked text does mention the more liable halogens giving lower yields and the lists other byproducts formed, at least to some extent, I'm thinking none are formed via the arylchloro route. Anyone's thoughts or experience on the FC alk's &/or halogenation of aromatic allyls with different halides would be most helpful in gaining a comparative understanding and useful strategies in both optimisation of procedure, yield, and recovery of useful byproducts.

There's some discussion of this in:

https://the-collective.ws/forum/index.php?topic=19504

and

https://the-collective.ws/forum/index.php?topic=14954.msg82752#msg82752

but it's probably not as complete as may bee desired  ::)  The end results from the effort applied  8)
« Last Edit: February 17, 2013, 06:10:26 PM by lugh »
Chemistry is our Covalent Bond

Doc B

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #69 on: February 17, 2013, 09:42:08 PM »
Thanks Lugh but I can't log in to the collective to view.

lugh

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #70 on: February 18, 2013, 02:22:36 AM »
Thanks Lugh but I can't log in to the collective to view.

That sounds like a personal problem as the member there with the same nym hasn't logged on since the end of last year  ::)  The end results from the effort applied  8)
Chemistry is our Covalent Bond

fishinabottle

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #71 on: February 19, 2013, 03:03:58 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?

Do you have a ref for the CaOCl2 on Manganese actetate? That would be nice?
In one of the papers on electrolytical Mn(III)Ac they stated they could not use ammonium nitrate as electrolytic salt for it decomposed immediately thereby oxidising the Mn(II) to the Mn(III).
Doesn't this, so cute and casually mentioned ring a bell? For sure the nitrate beats KMnO4 in solubility and not only there.....
The problem to be solved with the Mn-Acetate is that it would call for permanent extraction of product to get volumetrically interesting.
And thats not the the route which would benefit greatly....

So I call out for all information useful to extract P2P from an (anhydrous) reaction. The Kilomentor blog names inmobilized semicarbazone but thats a problem in itself sadly.

/ORG

Doc B

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #72 on: February 23, 2013, 06:12:28 AM »
Dear Sir Orgy,

I regrettably advise that I am unable to locate, thus pass on the ref for CaOCl2 oxidation rxn as you requested. The effect of which I might add, is not limited only to my subsatisfactory inability to provide you with. I appeciate that you have taken time and effort to comment upon an interesting rxn that has my intreset.
It is, with possible soom dread that id continue search and incidentaly descovering the root cause proof of the failure pinned upon miscommunication in lit. ref. Oh how horrid and embarrassing! Imagine an unsuccessful synth attempt for muddled lits, I doubt I could bare the shame. If I can though and find fault where I now suspect perhaps there may have been, it may be a boon for the revision and reconsideration of the entire rxn. As I am utterly confounded to the absence of ref. I was sure than only 12months or so ago did I have it at hand, I looked it up follow quiery upon the first failure at oxidizing. The ref. was then applied to a several molar attempt without micro scale proof of principal, in a land where even common reagents are more costly than many would possibly imagine. If the resulted in the planning and subsequent attempts to oxidation of Mn3(OAc)3 upon two costly and unsuccessful occasions was such a ballz up, I may need to suggest to a certain someone that retirement and a good death are the wisest priorities given the failing cognitive and proble solving abilities inherent in their elderly age.  :o


Doc B

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #73 on: February 23, 2013, 01:41:30 PM »
Pardon my tardiness, Ive only just reread your comments with a clearer head. Are you suggesting the paper, I recall the tables and comments you refer too, imply a chemo oxidation occured addition of NH3NO2? That the respctive electrolyte's physical properties alone allowed the conversion of Mn(II)->Mn(III)?

That would be pretty um..... Hehehehe fucking awesome! Although KMnO4 and NH3NO2 are in even the most basic lab the previous failures have governed the altered tact away from the course sailed previously.

fishinabottle

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #74 on: February 23, 2013, 08:35:22 PM »
Pardon my tardiness, Ive only just reread your comments with a clearer head. Are you suggesting the paper, I recall the tables and comments you refer too, imply a chemo oxidation occured addition of NH3NO2? That the respctive electrolyte's physical properties alone allowed the conversion of Mn(II)->Mn(III)?

That would be pretty um..... Hehehehe fucking awesome! Although KMnO4 and NH3NO2 are in even the most basic lab the previous failures have governed the altered tact away from the course sailed previously.
Yes. Thats why I mentioned it.

/ORG

Doc B

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Re: 1-Phenyl-2-Propanone synthesis Overview.
« Reply #75 on: February 24, 2013, 12:19:22 AM »
Damn, thank you Orgy!

How many times has that gem been read, reread and glazed over? Perhaps it's just me.

Sir, you are both a scholar and a totally awesome gentleman! Thanks for the prompting ever so much. You're twice this week a beacon illuminating my dark ignorance. I think I ought to send you an ACME pH meter, in appreciation and as a gag! PM and it shall be done. ????