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Author: Subject: Phenylacetic acid from styrene, sulfur and ammonia
Hexabromobenzene
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[*] posted on 21-5-2021 at 08:01
Phenylacetic acid from styrene, sulfur and ammonia


Autoclave volume 3L made from stainless steel tube 100mm diameter and wall thickness 5mm with MMA welding. Threaded tubes 1\2 welded to it. DO NOT USE COOPER AND ALUMINIUM ALLOYS FOR THIS SYNTESIS
Into autoclave put 500ml styrene 1100ml 25% ammonia 450 gr sulfur. After filling autoclave closed with wrench PTFE lent was used. Autoclave placed on water bath 95C at 5 days with break at night. Every 1-3 hours autoclave stirred by hands.

After 5 days at water bath autoclave was opened. Lower organic brown layer separated and washed with water. Autoclave washed with detergent.

In 1.3 liters of water dissolved 350 gr sodium hydroxide. Sodium hydroxide solution and autoclave tar placed to the stainless steel boiler with 1 meter 2/3 tube(reflux) and boiled 2 days with break at night.

After boiling in mixture added 300ml xylene and upper organic layer was separated. In water layer added 2 liters 15% hydrochloric acid

DANGER!!!Lots of hydrogen sulphide evaporated its jets are visible. In room all cooper things was turned black.

After filtration and washing 190gr wet impure phenylacetic acid was prepared. If after filtration acid water solution was extracted and saturated sodium chloride(50-100 gr liter) with toluene can be obtained about 10-20gr phenylacetic acid. Phenylacetic acid contaminated sulfur and needs in separation with ethanol as example.

Willgerodt reaction with styrene and ammonia gives low phenylacetic acid yield(Not more 30-35%)

Warning! Autoclave tar has a very unpleasant odor in very low concentration which is very persistent
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[*] posted on 21-5-2021 at 10:39


Hmm, interesting - Do you have any photos?
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[*] posted on 21-5-2021 at 12:45


Quote: Originally posted by SuperOxide  
Hmm, interesting - Do you have any photos?

No

Notes:
Carbon steel can de used as autoclave material(fire extinguisher or tube as example. YOU MUST NOT USE BRASS OR ALUMINIUM PLUG ). In first experiment i used carbon steel tube from old plumbing 1/1/2 with inner diameter 40mm and 3mm wall thickness. But it slowly corrodes. Also desirable add sodium carbonate to water bath to prevent corrosion
Autoclave tar(organic layer) contains some free sulfur. To get rid of it you can keep it several days.
Autoclave tar contains many organosulfur compound(diphenyl thiopnene and thiophane main) and tars. After extraction phenylacetic acid about 1/2 tar is not dissolve in water alkali
350gr alkali is much. 200gr enough
Adding ethanol in reaction mixture may increase yield, but part phenylacetic acid amide gone into water layer ammonium polysulfide and its necessary evaporate(ammonia and hydrogen sulfide released) and wash from sulfur with ethanol.
Ammonium polysulfide solution can be used again if add half sulfur and 1/4 ammonia. Or it can be evaporate to recovery sulfur. I recovered about 100-150 gr sulfur from 450-500 gr initial.
If you want prepare P2P from this acid by pyrolysis with acetate you MUST clear phenylacetic acid from sulfur. Sulfur reacts with phenelacetic acid at high temperatures. Very much hydrogen sulfide formed(brass fittings turned black)
[Edited on 21-5-2021 by Hexabromobenzene]

[Edited on 21-5-2021 by Hexabromobenzene]
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[*] posted on 21-5-2021 at 23:35


Yeah. The literature suggests that when styrene is utilized in this reaction, LOTS of Hydrogen Sulfide is generated.

Earlier posters have indicated that the presence of Isopropyl Alcohol, improves yields substantially.

I've seen papers claiming higher yields. 95C seems like kind of a low reaction temp.

You might utilize the search engine to examine alternate procedures.

There was a recent posting on a similar subject.

https://www.sciencemadness.org/whisper/viewthread.php?tid=15...

Discussing the Willgerodt is OK. If this becomes a P2P--> Meth discussion, quite likely it will be purged.

[Edited on 22-5-2021 by zed]
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[*] posted on 26-5-2021 at 12:54


Hydrogen sulfide evaporate if you add acid at soduim phenylacetate solution because it contains sodium sulfide. Also hydrogen sulfide stands of if you evaporate ammonium polysulphide solution for recovery sulfur/
If you make reaction at low temperatures(100C) pressure is low about 5-10bar. But main reaction product thioamide. If you make reaction at high temperature(150-180C) pressure high(20bar) and main reaction product amide phenylacetic acid
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[*] posted on 27-5-2021 at 19:42


Hydrogen Sulfide is bad shit. Getting rid of it is important. Evaporating it seems like a bad idea.

H2S being more toxic than cyanide is an issue. Some hydrolyse the Thioamide with Ammonia solutions, others with a base like NaOH. The former produces Ammonium Sulfide. The latter, produces Sodium Sulfide. Either is less toxic than H2S.

An interesting reaction follows; it seems like it might get rid of the Sulfide Ion completely, by oxidizing it. Though the authors aren't clear on the subject; it appears that they are oxidizing the Sulfide to Elemental Sulfur, while converting the Thioamide to an ordinary Amide.

Reaction of Thioamide with H2O2/ZrCl4. http://www.xiuzhengrd.com/ejournals/pdf/synthesis/doi/10.105...

[Edited on 28-5-2021 by zed]
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[*] posted on 28-5-2021 at 02:32


H2S should be immediately bubbler through a solution that will immediately destroy it like naoh solution or even better metabisulfite which apparently turns it back to elemental sulfur. Anything less than this is risking death. Even attempting to burn the gas probably won't be foolproof and still leak H2S into surrounding areas.
What does bubbling h2s thru h2o2 equal? Is it sulfuric acid or sulfur or nothing?
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[*] posted on 28-5-2021 at 03:50


/CJ

Attachment: The Willgerodt-Kindler Reaction - Part I.pdf (1.8MB)
This file has been downloaded 382 times





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[*] posted on 28-5-2021 at 09:31


Problems uploading Part 2..... This will have to do for now.

https://anonfiles.com/l5Y1y9yau5/The_Willgerodt_Kindler_Reac...



/CJ




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[*] posted on 28-5-2021 at 10:13


So, over 48h of constant boiling + another 24h produces 35% yield? Considering that it's pretty much one-pot, could be indefinitely scaled up and leave unattended for the most part, it could be viable.

But, the people wanting so bad PAA, turning it into a certain ketone, the next step is no less hazardous and arduous at the same time, and ultimatum, it produces no higher yield than that neither. So, from 1kg of styrene, one will obtain about 100 grams at most.

I know, I'm a party pooper. Just had to think it out loud. :P
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[*] posted on 29-5-2021 at 00:59


I've seen procedures claiming yields of Phenyl Acetic Acid in the 90% range.

Yields of Ketone from Phenyl Acetic Acid up to 70%.

The Wilgerodt is stinky, possibly perilous, chemistry. But, Styrene is dirt cheap, and available in trash where I live.

I could salvage hundreds of kilos of Styrene Polymer, just from 4th of July Picnic waste, discarded at local parks.

I don't fancy embarking on such a project, and I don't think it would be a nice thing to do, but would it be practical?

Yeah.

Too bad Methamphetamine isn't a cure for COVID. Although, come to think of it, do you suppose it has had a clinical trial?
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[*] posted on 29-5-2021 at 03:32


I've seen those too, but a question remains, if the numbers are inflated? Haven't seen any reputable studies of the matter. Anyway, I nowadays use to mark yields down, because in the end, what you get after purification steps matter, not what you should have gotten. There's no god of chemistry that can annex missing yields if you have high exp lvl in chemistry and some good rep points. Sadly.

And yes, styrene is indeed available, directly as a monomer dirt cheap too, as it is used in glass fiber resin. They sell it in 1L, 5L, 20L and 200L sizes here starting from few € a L, more you buy the less. I would mind more about sulfur, though, as it is otc as fertilizer somewhere, but I have never seen any. Ammonia is easily and cheaply made in bulk from urea hydrolysis, so that is neither an issue. Styrene has 10 times lower odor treshold than toluene, btw, and although the odor is not bad, even a bit pleasant in minor quantities, it gets really overpowering at any bigger amounts.

Most clever idea would be to think it all the way through and weld at least two valves into the vessel, so that once it is ready, it can be readily flushed with gas to extract any generated H2S. Opening it manually would be extremely dangerous.

Now that I think, I remember seeing a chinese patent about it, and they used ethanol as a solvent with all the added stuff, with higher yield of acetanilide.
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[*] posted on 30-5-2021 at 21:07


Quote: Originally posted by zed  

Yeah.

Too bad Methamphetamine isn't a cure for COVID. Although, come to think of it, do you suppose it has had a clinical trial?


America has a proud tradition of stimulant abuse. Basically one of the few things that we as a nation seem to rally behind. Surely, we would have figured out this curative aspect of our national pastime by now if it existed.

Now, I do have a question regarding the use of styrene for another synth that isn't worth a new thread. If anyone has experience, I would like to know if it is more time/energy/labor efficient to isolate styrene monomer from car repair "bondo" or to get it from polystyrene cutlery? There seems to be a number of additives in bondo that may prove difficult to separate.
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[*] posted on 30-5-2021 at 23:10


I would absolutely not bother extracting styrene from anything. Also, EPS needs solvent to reduce its volume, and plastic pyrolysis is very dirty and is not quantitive and needs redistillation. Uninhibited styrene monomer can also polymerize spontaneously.

For PS cutlery, the cost for 1kg of styrene would be likely hundred $ + labor.
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[*] posted on 31-5-2021 at 02:32


Quote: Originally posted by zed  
I've seen procedures claiming yields of Phenyl Acetic Acid in the 90% range.

Yields of Ketone from Phenyl Acetic Acid up to 70%.

The Wilgerodt is stinky, possibly perilous, chemistry. But, Styrene is dirt cheap, and available in trash where I live.

I could salvage hundreds of kilos of Styrene Polymer, just from 4th of July Picnic waste, discarded at local parks.

I don't fancy embarking on such a project, and I don't think it would be a nice thing to do, but would it be practical?

Yeah.

Too bad Methamphetamine isn't a cure for COVID. Although, come to think of it, do you suppose it has had a clinical trial?


I wondered when covid first came around if ephedrine or amphetamine
would help ease covid Symptoms the way it helps with colds and flu.
I still don't know if anyone has tried testing this theory
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[*] posted on 1-6-2021 at 00:42


The depolymerization/pyrolysis of Styrene is extraordinarily cheap, easy, and high yielding. Tracking down and buying pure Styrene Monomer is more difficult tha it used to be, and more expensive.

In the USA, Styrene cutlery is dirt cheap. Maybe a few dollars for 500 grams, and it is disposable.

I could easily produce a Kilo of monomer in an afternoon, just from trash.

Here, our friend UC235... Shows us how easily this un-making can be achieved. Utilize a polymerization inhibitor if it seems appropriate.

https://www.youtube.com/watch?v=6tEs7P6UUVQ
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[*] posted on 1-6-2021 at 07:58


In here, getting polystyrene plastic cheap in bulk is difficult, while styrene monomer is sold otc at several locations at cost I earlier referred. It is also available in ordinary HW stores and even in some big-box stores, but is sold in smaller, 400mL or similar canisters and commands a significantly higher price tag.
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[*] posted on 1-6-2021 at 08:23


It sounds like a regional difference, then. I've never seen styrene monomer for sale in the US. On the other hand, putting on some rubber gloves and raiding the trash cans at a public park, as zed suggested, will make you look like a lunatic, but you will certainly be able to recover significant amounts of polystyrene trash in a single afternoon, with the only cost being your dignity.

If any concerned bystanders ask what the hell you're doing, just say you're experimenting with a method to recycle it. It wouldn't technically be a lie.

[Edited on 6-1-2021 by Texium]




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[*] posted on 2-6-2021 at 11:55


Well, I checked at the local stores a while back. The liquid plastic casting material in this area, is a mixture of Styrene Monomer and Polyester. And, it ain't cheap. It's a specialty product.

Styrene eating utensils are mass produced, and widely distributed. Cheap. Every grocery store sells them.

Petrochemicals and petrochemcal products, aren't very expensive here. I was mildly irritated at paying $3.19/Gallon for Gasoline yesterday. A little more expensive than the price of milk.

A U.S. Gallon is about 3.8 Liters.

Technically, Styrene shouldn't be too much more expensive than Gasoline. Provided that you buy enough.

[Edited on 2-6-2021 by zed]

[Edited on 2-6-2021 by zed]
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[*] posted on 2-6-2021 at 13:23


https://fiberglasswarehouse.com/styrene-monomer

Isn't this what you're looking for? Google'd "glass fiber resin styrene price usa" and it gave various results. Styrene is used in laminating glass fiber fabrics into structures like boats and stuff. I've made a couple of boats with my father almost 2 decades ago, and when I needed some styrene in my chemistry, it was some nostalgic smell. :P

5 gallons, about 3.8 liters each, makes 7.7$ per liter, for 19 liters.
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[*] posted on 2-6-2021 at 15:30


WHAAA????????????????? CHEMICALS NOT IN STORES ARE AVAILABLE FROM THE INTERNET?
BRILLIANT!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!WHO KNEW???????????????????????
THE MORE YOU BUY, THE CHEAPER IT IS???????????WOW!!!!!!!!!!!!!!!

Well, that's how I feel. Sane people probably think I shouldn't wear my emotions on my sleeve.

And congratulations for telling LE and FW that their product is officially associated with meth manufacture. You're doing everyone a great service.

If one really wants to be Walter White, it would be best to figure out how to make things the right way instead of wasting time making tar. Or go back to pills and RP/I, clomethiazole, or MDA from bleach. If this method was all that, I'm sure Uncle Fester et al. would have let us know a long time ago.

[Edited on 2-6-2021 by S.C. Wack]




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[*] posted on 3-6-2021 at 02:38


The UN conventions have already listed all major drug precursors 50 years ago. There are professional forensic chemists consulting LE in these. Sometimes it's easier to check from the lists if something might be worth looking into, instead of looking what's not watched, because bogus stuff doesn't have to be watched, it's even better that crooks waste their time attempting stuff that is doomed to be failed. And don't forget forensic documents, which sometimes basically state "look at these pathetic cooks, we, the forensic chemists, know things better, now, let me show you how it's done in a very simple and high yielding way".

U.F and other sources tend to state certain methods they have learned and found viable in their own circumstances, but they might not be by far the easiest, best yielding or even available at many other circumstances. Whatever chemistry I look into, I eventually come up with some source that presents a much more viable way to achieve a certain outcome. Also, the operations that matter, do make careful calculations to maximize the profit - even if something is available OTC, does not make something profitable. For example, pills cost so much that they will likely eat up most of the profit. 100% is very bad, these guys usually look at least one or two orders of magnitude of ROI. Put 1k in, get 100k out. At least those were the numbers of one large Asian ORC. And finally, when you really realize you're onto something, it immediately becomes proprietary, so, the most effective and fine-tuned methods never surface and are actually kept as secret as possible, and may never be actually written down anywhere.

When we go to pre-pre-pre-precursors, any legislation will basically become ineffective, because they consist of so essential compounds that just cannot be monitored by any reasonable degree. Majority of illegitimate pharmaceutical precursors are anyway imported in bulk from third countries, and it doesn't really make that big of a difference if John Doe can or can not buy his 10oz can of glass fiber resin thinner, but it annoys the crap out of the half a million hobbyists and boatbuilders and other who use it. On the other hand, you can always resort to dumpster diving disposable utensils, if it happens to be banned.
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[*] posted on 4-6-2021 at 04:19


At a certain point restricting chemicals just becomes impossible.
No matter what ammonia,styrene, ethanol, etc can NEVER be restricted
or scheduled. They are just too necessary & common. Caustic soda and HCL are found at every meth lab ever yet there's zero chance of them disappearing due to
gov restricting them.these pre pre precursors are just too necessary and widely used.
Those lists and gov restrictions can only go so far and there getting closer and closer to the point they can not restrict any further
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[*] posted on 4-6-2021 at 11:12


To be honest, I wouldn't swear on that. The concept of individual freedom is diminishing as we live, because it has a conflict of interest with security, which is a never-ending cycle.
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[*] posted on 4-6-2021 at 16:31


Things like bleach,pool acid,acetic acid,fertilisers,ammonia,caustic,styrene,thinners,btx,acetone/mek/yclohexanone,
esters,alcohols
Can NEVER become listed as it would literally stop consumerism/industry/cleanliness and lifestyle.they might be able to get rid of selling styrene to ppl otc and ban polystyrene single use utensils but polystyrene is here to stay which means styrene will always be one step away if desired.as long as ppl use paint, thinners/alcohols/btx Chems will be around,as long as cars are around btx/hexanes will be around, as long as ppl have swimming pools chlorine and HCL will be around,as long as packaging and surfboards are around styrene will be,as long as sugar and yeast and laws that allow alcohol to not be a schedule 1 narcotic exist alcohols will be around U see where I'm going with this.they CAN'T ban these things.

[Edited on 5-6-2021 by draculic acid69]
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