Polystyrene foam and acetone ==> P2P

[Shane_Warne]

It's a more worthy project than a biosynth, isn't it? More predictable.outcome.
 
I know a lot of bees here think that they're only capable of doing RP/I2 reactions, thus ephedrine is the only goal.

Polystyrene foam --(heat)--> styrene monomer--(95C, ammonia water, sulfur, EtOH)-->Phenylacetamide--(hydrolyze using base or acid)--> phenylacetic acid

Acetic anhydride comes from ketene produced by from tone and a ketene lamp. (UTFS for ketene)

phenylacetic acid + acetic anhydride ==> P2P

P2P + Al/Hg salt and methylamine ==> Meth

Post 495436

(tweekdexter: "new preparation of phenylacetic acid", Chemistry Discourse)

Post 258134 (missing)

(foxy2: "New preparation of phenylacetic acid", Chemistry Discourse)

What do you bees say?

[cycosyince]

So there is a smattering of interest, yet the other curiosities beg to bee addressed, such as: Little detail as to have you actually run this synth?
What kind of problems are inherent with it?
What kind of ratios/yeilds are we gonna find?
What kind of time is involved?
how much equipment will it require?
Can it be done ala ghetto without an added risk to factor?

Impress the bees with the rundown, not just a tease...
VE could learn you a thing or two about throwin down new techniques on the forums.

YOU have the floor,
we're waiting...

[Shane_Warne]

If you sink, and surely burn.

If you had read the experimental you would have discovered a 60% yield of phenylacetic acid from polystylene is really, realistic.


The downsides are smell at various stages. WizardX said that the smell of sulfur, during the step from styrene monomer to phenylacetamide would bee quite disturbing.

But it's unclear to me whether WizardX considered sealing the vessel as the guy in the experimental did.


The time factor is dependent on your knowledge and workmanship. It could take monthes, or it could take years.

What kind of ratios/yeilds are we gonna find? Read/UTFSE

Can it be done ala ghetto without an added risk to factor?

Hard to say. purifying the styrene monomer requires fractional distillation, but because it's acidic, I doubt a copper setup would suffice. We have to investigate this. So ar you gonna help or just bee a dick?
The methods are very well established, we just have to work out how to make them suitable for us.

Turning the styrene monomer in to phenylacetamide, and then on to phenylacetic acid, one of the two main ingredients to P2P requires no lab equipment, as you would discover if you had clicked the link I searched for YOU.

Al/Hg requires Aluminum sheet, either foil or Al from cans that have been well cleaned (sanded).
Hg from mercury that has been treated with chlorine gas. small amounts of the Hg salt are reuired for reductive aminations.


Buying pills is a trap. Whether one does it him/herself or has a whole hoard of people buying them.

The smart money is on P2P.

Oh and it's not a write-up, it's a life-line. But VE is welcome to add to our project.

Come on, don't be a fag nowe, we require a ghetto method for phenylacetic acid, and acetic anhydride. Both have been described here at The-Hive first hand.

Ill keep reading.

[ApprenticeCook]

Buying pills is a trap.

Getting that way.... so yes i do agree buying eph is going out... p2p needs to be the way to go...

This sounds too good to be true... but reading the info it sounds rather good and not too hard...

[Organikum]

Styrene monomer is in polyester resin - usually 40% to 60% depending on the manufacturer, no need to pyrolyse polystyrene.

On my desk before me sits a box of usual car-repair polyester resign, 242gram. It says: 46% styrene content, which should be easily recovered by plain distillation, whereby it is questionable if this is even necessary for the following sulfur treatment - the mix contains probably some polymerization inhinbitors which might come handy.
With the box come about 8 gram dibenzoylperoxide a polymerisation catalyst which is useful as a radical initiatior in many other synths (chlorinations based on radical substitution mechanism for example, like toluene to benzyl/benzalchloride and more).
It wont be 8 gram peroxide plain, but X gram + solvent of course but this wont matter much for the intended uses.
Both, resin and radical initiator can be bought as single compounds. Even styrene pure as solvent for plastics is available for everybody who looks around a little bit. It is not forbidden to build oneself a surfboard by now.


hope this helps
ORG

PS: Before doing the pyrolysis of acetone I would suggest to have a look into the reactions of acetic acid and phenylacetic acid to yield P2P. This seems to me favorable over acetic anhydride pathways.

[xxxxx]

i once saw a quart of pure styrene monomer for us$10. for the wilgerodt a high boiling amine can repace ammonia. once you have phenylacetic acid consider maybe ethyl phenylacetate condensed by sodium ethoxide with ethyl acetate in ethanol then saponification and decarboxilation to form p2p?

[WizardX]

The downsides are smell at various stages. WizardX said that the smell of sulfur, during the step from styrene monomer to phenylacetamide would bee quite disturbing.

But it's unclear to me whether WizardX considered sealing the vessel as the guy in the experimental did.

At some point you must open the reaction vessel to work up the reaction mixture. This is where the pungent sulphur smell is.

[ApprenticeCook]

sulphur is rotten, so thats a problem but what about yields etc??? is this process worth the smells it produces by creating some nice clean p2p (after disto) in decent yields?

[WizardX]

PHENYLACETAMIDE:

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv4p0760

Phenylacetamide has been obtained by a wide variety of reactions: from benzyl cyanide with water at 250–260°;5 from benzyl cyanide with water and cadmium oxide at 240°;6 from benzyl cyanide with sulfuric acid;7,8 by saturation of an acetone solution of benzyl cyanide with potassium hydrosulfide;9 from benzyl cyanide with sodium peroxide;10 by electrolytic reduction of benzyl cyanide in sodium hydroxide;11 from ethyl phenylacetate with alcoholic12 or aqueous13 ammonia; from phenylacetic acid with ammonium acetate14 or urea;15 from diazoacetophenone with ammoniacal silver solution;16 from phenylacetic acid imino ether hydrochloride and water;17 from acetophenone with ammonium polysulfide;18 from benzoic acid;19 by heating the ammonium salt of phenylacetic acid;20 and by heating cinnamic acid with a mixture of sulfur and ammonium hydroxide.21

[Shane_Warne]

Organikum, your right, styrene momoner is out there in resins and readily available, as is every other ingredient.  

Post 489377

(Organikum: "Another way to GAA", Chemicals & Equipment) Acetic acid from vinegar... A better method
GAA (Glacial acetic acid) from acetone vapour decomposition to ketene, using a Cu tube and a burner, then bubbling the produced ketene through a 70C solution of vinegar, to form acetic anhydride, hence reacting with water to form GAA, simultaniously distilling off acetone that isn't successfully decomposed by the pass.

ORG is there any problems with this setup, that swiO has discovered?

Flash back problems when the acetone exits the aspirator tube and the GAA reaches a flammable concentration? (despite the vacuum)

The connection from the end of the bubbling tube to the vinegar flask (?) sounds like it would need more than a rubber stopper, any ideas?

ORG your right, a route from acetic acid would be preferable and more straight forward. I mean, the route from acetic anhydride isn't bad by any stretch of the imagination, and is worthwhile and realistic, but concentrating a solution of acetic acid is just more straight forward.

Also if you have phenylacetic and GAA you can use any procedure which use phenylacetates and acetates too, which don't require high temperatures, if one has that limitation...

Post 23796

(Mastermind: "Re: P2P", Methods Discourse)
'...A mixture of PAA and acetic acid was passed through the tube at around 400-450C ... P2P'

WizardX, thanks for dropping by to say that. I just wasn't sure if you had considered a sealed vessel or not.

WizardX and ApprenticeCook,  perhaps we could consider cooling the vessel down to room temperature, and then freezing the vessel before work-up to lower the sulfur stench.

There's always a fumehood too.

Ill dig up the yield numbers, what numbers do we need need...

from acetone -> acetic acid or to acetic anhydride
from styrene monomer --> phenylacetic acid
from phenylacetic + acetic acid OR acetic anhydride --> P2P
from P2P -(Al/Hg)-> Meth

What about the yields of P2P using acetates and phenylacetates that you can make with your acids, are you guys interested in those too?

We can way them up then.  

I'm pretty sure I2 or KI from RPI can be used to form a Hg salt too btw, instead of Cl, so there's no worry about Cl gas, and it's just neater.

[Organikum]

Yes, I was referring to masterminds tube with MnO catalyst, this plain eliminates one step (acetone to AA) and is IMHO favorable.

The use of the mercury iodide was covered already but not everybody got it going as far as I remember.

[ning]

I wonder what would happen if one were to add H2O2 to the reaction vessel and stir well before opening it.

H2O2 will oxidize sulfide ion to elemental sulfur. It is used industrially to do this in the treatment of wastewater and sewage. It shouldn't have much effect on the phenylacetic acid.

This will also make the workup hydrolysis not emit poisonous H2S fumes, hopefully. An important factor for the larger-scale cook.

[Chewbacca]

such an idea would also be useful for any other reaction in which a side product is H2S.. bubble into H2O2.

[Organikum]

Also if you scavenge the sulfur stink from hell - there will be always left the sweet smell of phenylacetic acid. "Sweet" is of course relative. VERY relative.

[Shane_Warne]

Ning: The H2O2 sounds good!

The yields are extremely high to phenylacetic acid, well in the patent that ning translated in the other post it is reported as such. Ill paste it here to help with organisation.

In a reaction vessel was placed:

Styrene 21.7 g
Sulfur 37.6 g
Ammonia 50 ml
Ethanol 30 ml

'Under stirring and heated at 93-95 C for 3-4 hours. Fluids were evaporated from the mixture, it was allowed to cool, and extracted 3 times with 500 ml hot water. The decolorized solution after standing yielded 26.7 g (97%) white sheets having MP of 157-158 C and BP of 280-290. (Phenylacetamide C8H9NO)

100 g of the above phenylacetonitrile and 80 ml HCl were added to 150 ml water and refluxed for 2-3 hours. After cooling to room temp, a precipitate formed and was filtered and recrystallized from 1:2 ethanol/water to yield 84 g (84%) of shining white crystals. (Phenylacetic acid C8H8O2)'

So it works out to about 90% from styrene monomer to phenylacetic acid. That's fucken good for 2 steps and OTC ingredients.
Knock a big fat 30% off that, and we're really in the realistic (pesimistic) zone, and it's still very nice.

Ac2O (acetic anhydride) or AcOH (acetic acid) seem to be the hardest, and the most fiddle to setup an apparatus.

Dangerous too, ketene is deadly and flammable, but won't explode if O2 is absent (same with acetone)

Also although acetone is cheap, it isn't expendable IMO, and it wouldn't surprize me if it disappeared at some point. I hop not, but you have to plan for the worst.
So having an implementation in your aparatus to save acetone that isn't successfully decomposed is almost essential.
Dripping acetone on a glowing toaster wire inside a copper tube should do the trick. Bubble the ketene produced through a hot flask or jar of vinegar, fitted with a two-hole teflon-coated cork.
The 2nd hole leads to a jar sitting in ice to condense the acetone that distills off the first jar.
Still I've never done it, but that's where my thoughts start.

Oh, boys! I've got a phat surprICE for ya! If you can't acquire methylamine, or just don't want it around, you can have plain amphetamine from the Al/Hg, in high yields (96-98%), using only 25% ammonia water.      
See for glee:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/amph.alhg.html

Actually the yield at the introduction of this page is totally different to the experimental, at 30%. I'd trust the 30% as more realistic

The yields of P2P from PAA and AA, with NaOAc aren't very good, and a large excess of AA is used (to avoid useless dibenzyl ketone formation, it states) , but even then, 50% is optimistic.
Read for yourself here:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#phenylacetic

A longer reaction seems important for yields too.

ORG:
There isn't much info on methods that use acetic acid instead of acetic anhydride. Sure there's that Mastermind post, but what is that worth? What guidance is it? Ill try find more but I think it'll turn out to be more wise to put the effort in to acetic anhydride, don't you think?

[randolph_carter]

that is one way you "could" describe that smell!!!

if one is into dreaming about this particular molecule (paa) they should be prepared for the almost unremovable "sweet" smell that this compound imparts to almost everything it touches.....

wearing tyvek coveralls is DEFINITELY recomended so ya can burn em.....

all work surfaces should be covered with plastik for disposal....so ya can burn it.....

gloves will stink to high heaven forever so use , you got it, disposable gloves......so ya can burn em.....

this is one of the more tenacious smells that some swinoidz back in the day of paa-acetic anhyd-pyridine synths of p2p became quite adept at picking out...

i once overheard one of them referring to someone who had came in to the local zippy mart with that smell on them as "having the sweet smell of success..." and i read about the poor soul in the newspaper the very next week and it wasn't because of particapatin in a 4-h project why he was in the local paper...

just a lil heads up for people who are unaware of this issue....

YOU WILL GET IT ON YOU!!!!!
YOU WILL FIND IT VERY DIFFICULT TO REMOVE FROM YOU!!!!!!
SWINOIDZ DO KNOW WHAT THAT FUNNY SMELL IS AND WHAT YOU MAY BEE DOING WITH IT!!!!!

just take appropriate precautions to avoid this problem....
fyi...

[Organikum]

you can have plain amphetamine from the Al/Hg, in high yields (96-98%), using only 25% ammonia water

Thats sadly not true.  
If you know a trick which makes this possible please tell! It would be highly appreciated.

For the rest: VERY GOOD! A real breakthrough!

ORG

[DrLucifer]

In regards to distillation of polystyrene, swim feels that a vital element is missing from discussion!
That is of course, the antipolymerization agent required for the final stage of the Polystyrene-->Syrene reaction.

Preparation of styrene:
A distillation setup was assembled and 100g of powdered scrap polystyrene was added and heated to 340 C or higher. The distillate over 340 C was collected and assumed to be styrene. Still, the color was rather crimson, and impure. The impure product was mixed uniformly with 5% by volume sulfuric acid and was left to stand for 3h to remove impurities, then rinsed 3 times with brine, dried with anhydrous sodium sulfate, added antipolymerization additives.
The portion boiling at 145-146 C was collected to yield 89 g (89%) styrene.

This text is fresh from translation, but you get the idea.
Now, whilst swims initial searches didnt fruit anything terribly useful, he did find out that methanol is incorporated into embalming fluids as an antipolymerization agent for formaldehyde.
Im not sure whether methanol would be suitable in relation to crude styrene, but swim figures it is worth trying.
Can anybody suggest a better antipolymerization agent?
Would different agents affect the boling point of the styrene?
Another question would be what concentration of H2SO4 is required in this process? Swim would assume that 5%/volume of 98% H2SO4 be used, but since its role is to remove impurities, perhaps more/less could be used depending on how well the initial distillation proceeded...
Now despite the styrene monomer being available commercially, swim feels the route from polystyrene would be more practical to start with!
What are bees opinions on this subject?

[Shane_Warne]

ORG, I'm looking at that experimental page again and I can't see the error in the reagents or the product.

phenylacetone (P2P) + Al/Hg + EtOH + ammonium hydroxide --> Amp!

The yields in the introduction don't seem to correspond at all to the experimental section, neither does the explanation on that page, about yields.

Is it the yields that aren't true, or the procedure just doesn't work, or have I missed something?


talking about it is the breakthrough.  

randolph, could you quantify the smell even further by comparing it, to say aromatic hydrocarbons and iodine?

Anyway, the task is worthy of an exaust fan and a carbon filter, but just for interest.

I can see what your saying too, there will be a smell because it states that the '...Fluids were evaporated from the mixture, it was allowed to cool, and ...'



DrLucifer, I don't know but I hope someone does.  no point in bullshitting on purpose.  

[weaz1dls]

Impresive, mostly over SWIW's head at this point. Did wonder if anyone was going to address the smell factor.  Will contact an old Bee who's old lady had some spray shit she would make. Sprayed  onto surfaces in hotels it nutralized that shit.  SWIW is sure someone here could figure it out.  Ok enough cave chater Swiw will read up here and attempt to get on the same page.  Any 101 links PM'd in relation to the mechanics would be helpful.