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Author: Subject: Willgerodt rxn: Styrene monomer -> phenylacetamide
Nicodem
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[*] posted on 31-8-2006 at 11:20


Sincerely I'm not sure anymore if you understand where the pressure comes from. If is not from the gases evolved because of the reaction. It comes from the:
  • ammonia in the reaction mixture solution which at 95°C is already well above the saturation point and consequently equilibrates by increasing its partial pressure above the liquid phase;
  • the partial pressure of the ethanol (or isopropanol) cosolvent that at atmospheric pressure boils at a temperature lower than 95°C even when diluted by water and ammonia;
  • partial pressures of water, styrene and other volatiles;
  • partial pressure of the air that was left inside when closing the vessel.
Now, as you see you certainly don’t want a valve to moderate or vent the pressure out as this means you would loose the precious ammonia and ethanol, both of which concentration also determines the speed of reaction.
All these listed factors increase the pressure to about 3 bars (my estimation based on experience from similar examples) which is quite low and could be contained even by a simple PET bottle if it wasn’t for the temperature softening the polymer. What I’m saying is that even though you are such a tenacious DIY guy, you don’t really need to go as far as mounting a valve and all that funcy stuff on the bottle. Just use a champagne bottle (which are said to stand the min of 20 bars, IIRC), a champagne bottle stopper and wire the stopper very well so it won’t pop out before its time to celebrate. Immerse the bottle for up to 3/4 height in water bath and heat the bath slowly (glass does not like sudden changes of temperature).
I have heated this way saturated solutions of NH3 in isopropanol at 100°C for days in normal 100ml Fluka bottles without troubles as long as the stopper was well fixed.
I’m truly sorry if I disappointed you, but this reaction is nothing special and does not require anything really special. The only reason people prefer to talk a lot about it, but try it not, is not because it would be difficult or complex like Chinese writting, but simply because they are lazy, mentally and physically (actually mentally mostly).
But look at its bright side. You can even have fun emptying the champagne bottle. :)

Edit: According to this site: "Today, the dark green Champagne bottle is designed to resist a pressure of 12 atmospheres..."

[Edited on 1-9-2006 by Nicodem]




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[*] posted on 31-8-2006 at 23:58


I'm seconding Nicodem, and adding that with styrene having a vapour pressure of very roughly 200 mm at 100 C, you'd best be real careful in the selection of any plastics exposed to those vapours; styrene is a pretty good solvent for organics. Use a real cork stopper.

Rather than evaporating everything off, you might be able add some water, warm to near boiling (of alcohol), filter to remove styrene and polystyrene, distill the alcohol off from the filter, add NaHCO3 until all of the free acid is in salt form, cool and filter to collect the amide.
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[*] posted on 2-9-2006 at 03:06


Thanks all I appreciate, I think we've well and trully sorted out how to conduct this experiment - the only thing left is to conduct it.

At the moment I'm washing some dusting sulfur with H2O then we can tread farther.
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[*] posted on 2-9-2006 at 04:39


You'd best pay attention to what's been said and forget about modifying a champagne bottle in too complex of a manner :P It should serve the purpose using the original stopper as long as it's heated and cooled slowly :cool: Complications are fine when they work, but the old time tested rule about keeping things simple is still just as true as it was long ago even if it's not taught in many schools anymore :D



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[*] posted on 2-9-2006 at 06:02


True, well yesterday I inserted a wine cork (a champagne cork is nigh imposible to re-insert in to a bottle) about 2/3's into a wine bottle and the things pretty tight.

When it comes to the crunch Ill use a wooden mallet to jam the cork in.

Is the pressure in the apparatus sensitive to how high I fill the bottle i.e the amount of reactants?
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[*] posted on 2-9-2006 at 12:42


It would be best not to fill it up all the way as doing that would increase your chances of failure :P



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[*] posted on 15-9-2006 at 18:15
willgerodt


Quote:
Originally posted by visitation123
Information on this reaction is quite difficult to track outside the Hive, did anyone keep notes on it?

It involved styrene monomer, NH3 solution, ethanol, and H2O from memory.


contact beebo at wetdreams ...
we have extensive personal notes including:
vogels excerpts, the hive archive, and safety addressed


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[*] posted on 16-9-2006 at 02:29


BTW:
Some time ago I made (few times) reaction aceotpenone/S/morpholine (without any acid calalyst). After hydrolize of reaction products and purification, about 50% theoretical amount of PAA was obtained :( Some says it should be not less than 90%.
But acetophenone is exepensive, so in future experiments I try to use styrene from depolimerization of polystyrene. Yeld of monomer is ~90%, they say (an article from SD says :)). Without pressure vessel only morpholine works good, giving high yelds of thiomorpholides.

[Edited on 16-9-2006 by kmno4]
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[*] posted on 12-11-2006 at 10:21


kmno4:

Literature gives divided reports on efficancy of reaction... But hey... 50% isn't so bad... I wouldn't say acetophenone to be very expensive at ~20$ per litre... Maybe MW would help the rxn...

If you have access to morpholine you could also try using styrene (paint thinner at ~3$/litre). The only drawback i see are harsher rxn conditions and smelly styrene (The closed can smells even if closed in plastic bag...) Also styrene doesn't keep well (likes to polimerize)...


In my search for cheap "high" pressure reaction container i have found that slightly modified old N2O containers work ok for nano scale rxns... The only drawback here is the oxidation of the inside of the container (it seems to be some kind of steel)... Also for this type of rxn sealed glass test tubes work (tried EtOH+S+NH4OH+Acetone ~100 deg C). But if using glass you should always keep them in some kind of blow container, in case the tube explodes... I use short piece of plumbing, loosely capped (you can get precut pieces and caps in plumbing shop)...

Will post some reports shortly :)
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[*] posted on 12-11-2006 at 16:11


try using styrene (paint thinner at ~3$/litre).

Don't you mean resin thinner? I've never seen styrene sold as a paint thinner.
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[*] posted on 21-11-2006 at 22:01


I think it's thinner for some kind of polystyrene based car color or sth. like that...
Don't know exact content of styrene, but it is the only thing on the label so there should be a good amount of it...

The N2O containers are suitable only for nano rxns... but this time i tried the rxn in sealed glass tubes, to avoid any problems because of metal reactor (there shouldn't be any even with metal)...

There were 2 tubes one with EtOH as solvent and the other with IPA, ratios according to chinese patent... I have also done some quasi-willgerodt rxns with acetone and MEK.

I first tried the MW method but soon stopped, because there was too much pointed heat and heating also seemed to be wery quick. I think my self-sealed tubes wouldn't take much heat-stress. At this point (30s MW in a glass of water) the IPA tube was already slightly yellow, which might prove IPA to be a better solvent, if it was not involved in some kind of rxn. I think that it doesn't react, as there are references of its use in willgerodt-kindler...

Then the tubes were heated at the bp of water for 3h... Now the content of tubes is a reddish liquid and on the bottom is something yellow, covered with a thin layer of oily liquid... My question is which is the product and what is the yellow powder at the bottom? I guess the oily liquid at the bottom is salted-out alcohol or/and unreacted styrene. The yellow powder is more puzzling, as it resembles the inital sulfur in the reaction, but if you look closely it is a bit shiny, which would suggest some kind of crystal structure... Should all the sulfur react to form polysulfides?

pics and analysis comming soon...
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[*] posted on 26-4-2007 at 10:43


The red substance is phenylacetamide.

Just going back to this discussion... a ball-valve or similar is highly desirable, as it allows for the safe piping of gases, especially and specifically H2S following the rxn to a bucket of H2O2 solution for example to convert or recycle the sulfur by forming elemental sulfur; but primarilly to avoid most of the toxic and pungent stench of the H2S.

A wine bottle just doesn't give you that option that I can think of, even if teflon fittings and tubing were used, there's a question mark as to whether they would withstand the ~5 bar pressures of the reaction - probably not.


tr41414, so do you know for sure whether a metal vessel (gas tank as I already suggested) can withstand a single run? I'd be surprised if it can't as Nicodem says.
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[*] posted on 26-4-2007 at 11:24


Quote:
Originally posted by visitation123
Just going back to this discussion... a ball-valve or similar is highly desirable, as it allows for the safe piping of gases, especially and specifically H2S following the rxn to a bucket of H2O2 solution for example to convert or recycle the sulfur by forming elemental sulfur; but primarilly to avoid most of the toxic and pungent stench of the H2S.

The amount of H2S that gets released when you open the bottle is minimal if you do things correctly. Most consumed sulfur ends up as ammonium polysulfide and only a little portion disproportionates to ammonium sulfide of which some hydrolyzes to H2S of which a negligible part escapes the solution. Still enough to smell it, but not more than that unless you do anything stupid.
Quote:
A wine bottle just doesn't give you that option that I can think of, even if teflon fittings and tubing were used, there's a question mark as to whether they would withstand the ~5 bar pressures of the reaction - probably not.

You were already told that it does withstand that pressure. Just don't forget to wire the stopper. Besides, the reaction never reaches 5 bars anyway.
Quote:
tr41414, so do you know for sure whether a metal vessel (gas tank as I already suggested) can withstand a single run? I'd be surprised if it can't as Nicodem says.

I never said that steel or other metal tanks can't withstand a single run. What I said is that it would be highly irresponsible to use if you value your health. If you would ask an engineer if you can use a steel tank for a reaction where polysulfides form he would have told you that you must be out of your mind. This however does not mean that the containers walls would disintegrate before you finish the reaction, they may or may not, though the additional consumption of sulfur and the contamination of the reaction mixture with iron sulfides would be terrible to deal with.

PS: Nice to see you still prefer to complicate instead of just doing the simple things. Some things never change. :P




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[*] posted on 26-4-2007 at 13:34


Nicodem, your smart and a fool at the same time.

Your going to have to boil or heat all those stinking fluids away during work-up, polysulfides reek too. Smell a bottle of "Lime-Sulfur". :P :D

I'm just saying something like a gas-tank has some characteristics which are conducive to a SAFER rxn and follow-up as opposed to a wine bottle.

But if you can't even guarantee it could survive a single run it isn't ideal at all.







[Edited on 26-4-2007 by visitation123]
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[*] posted on 26-4-2007 at 21:00


Quote:
Originally posted by visitation123
Your going to have to boil or heat all those stinking fluids away during work-up, polysulfides reek too. Smell a bottle of "Lime-Sulfur". :P :D

No need to continuously show your ignorance in the process you are so determined to use. You only need to evaporate the fluids if you don't know what you are doing. Do you even know how is that done? Do you even have a rotavapor? I guess not. Do you know how to use an aspirator to do that? I guess no or else you would not live in the illusion that you will have to smell H2S while evaporating these liquids. Besides there are simple alternatives to evaporation, but you would have to think about it to get to it.
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[*] posted on 27-4-2007 at 08:28


If you trully knew what you were talking about you'd know ammonium polysulfides are used in stink bombs I would have thought. :D

You have a lot of chemistry knowledge and useful knowledge in general, but you seem very proficient at handing out condescending remarks simultaneously with the other hand - I guess it's cultural.

Do I know hat a rotovap is? Yes
Do I have one? No
Do I know how to evaporate the reaction fluids in the steel vessel described? Yes....With an aspirator to hasten the evaporation of the fluids? Yes

Do I know how to evaporate the reaction fluids from a champagne bottle relatively quickly? Don't know never tried but with a barbed SS fitting it shouldn't be too difficult.

So are you going to tell me how you'd isolate the phenylacetamide without evaporating the reaction fluids as the patent calls for?

Having said that, the patents' leading the game 2-0 at the moment from memory...


P.S. try to forgive my ignorant attitude as you perceive it - it's cultural.
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[*] posted on 27-4-2007 at 12:26


That you think Chinese patents are more reliable than the literature methods already known and procedures that could be guessed by those with a clue is telling. It looks suspiciously like another example of the drug cooks thinking they've got it all figured out and organic chemists are clueless morons. One can distill off the ammonium polysulfide if desired but this seems without benefit over filtering and solvents if desired.

The red substance is phenylacetamide? What makes you so sure?
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[*] posted on 27-4-2007 at 13:41


Because, as it sounds you are unaware the reaction has been undertaken before and it was evauated to be phenylacetamide by people with more knowledge than me, and you.

Nice to see you listing the solvents for the washing and extractions, uh oh that's right you just came to invade a conversation, take one side and spill nonsense.

Yeah and it also seems that the reaction couldn't even be undertaken with the said compounds until I dug up the patent translation or that it can be EXTRACTED (not recrystalised Nicodem, that follows) with hot water. :D :P

Basically all I've learnt is that I was right all along as far as the reaction and work-up goes. Although I thank Nicodem for warning me about ammonium polysulfides and ferrous metals.

So I've learnt with vague, lazy descriptions that a champagne bottle might be implemented instead, that isn't too technically advanced, and certainly doesn't give either of you the intellectual high-ground.

Hmm, I think we shall stick with water extractions since it's clear neither of you are willing to detail further and rationalise use of filtering and washing, including solvents used and why. etc etc

Sorry, no time to chat about worthless theories etc.
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[*] posted on 27-4-2007 at 14:04


Come to think of it, your both wrong again.

Extracting and recrystallising with hot H2O then filtering is quicker, easier and cleaner for the environment than your methods using solvent washes. :P
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[*] posted on 27-4-2007 at 14:41


I never suggested the need for extraction with solvent, or even mentioned washing anything with solvent. It might be wise to recover a small percentage of phenylacetamide and all of the ammonium phenylacetate that may have been formed, but the majority of product can be obtained without solvent or distillation of the polysulfide.

It might be worth your while to look up the properties of phenylacetamide.

My bad for lack of detail on the worthless theories published by retard authors in JOC and JACS, and for not uploading such garbage to this wonderful thread. It has been uploaded elsewhere and that is enough for me.

If you want good advice, here it is: do it.
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[*] posted on 27-4-2007 at 15:25


So how do you imagine you'll ever isolate the substance?

I don't have my merck 13 installed, but i have it...well guess i am lazy :D

So you don't think the red layer contains the phenylacetamide or your unsure?
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[*] posted on 27-4-2007 at 16:34


Well, bad news folks, it looks like the Chinese patent was all a big joke/nasty prank. :D :D

Don't shoot the messenger.

The other person who tried it on a large scale (:D) got the same red substance as tr41414. It sounds as though it's worthless crap. :D

Physical State: Solid
Appearance: white glistening crystals.
Odor: Not available.
pH: Not available.
Vapor Pressure: 1 mm Hg @237 deg F
Vapor Density: 4.65
Evaporation Rate:Negligible.
Viscosity: Not available.
Boiling Point: 304 deg C @ 760.00mm Hg
Freezing/Melting Point:113.00 - 115.00 deg C
Autoignition Temperature: 545 deg C ( 1,013.00 deg F)
Flash Point: 173 deg C ( 343.40 deg F)
Decomposition Temperature:Not available.
NFPA Rating: (estimated) Health: 1; Flammability: 0; Reactivity: 0
Explosion Limits, Lower:Not available.
Upper: Not available.
Solubility: Slightly soluble.
Specific Gravity/Density:Not available.
Molecular Formula:C8H9NO
Molecular Weight:135.17

See we needed this discussion




Read this it's funny: http://www.synthetikal.org/hiveboard/arch/forum/topic/topic_...

Polverone tried this and seemed to think he had some success:

So now I'm completely confused as to whether this reaction is actually legit or not. My suspicion is not now.








[Edited on 28-4-2007 by visitation123]
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[*] posted on 27-4-2007 at 18:18


I posted that I was able to produce a uniquely foul-smelling something but I did not claim to have definitively produced phenylacetamide. I haven't done it again because the smell took forever to go away last time.



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[*] posted on 27-4-2007 at 22:12


Don't worry Polverone, you weren't the only one fooled (if that's what has occured). A whole host of Bees were, and a few made attempts.
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[*] posted on 27-4-2007 at 23:17


I wander why the hell did you even start this thread when already from the beginning it was clear you have neither a clue of what you are doing, neither the intentions to do any experiment at all. Is yours some kinky way of trolling or are you only trying to feed your greed by continuous requests for spoon feeding. Get this into your head: greed is great for wishful thinking and masturbation but is not good enough for success in real world!
I refuse to give you any more information that can be found in libraries or by using common sense coupled with what you learn in elementary school. I have no objections if someone else does that, it is just that I simply gave up. Sorry, I just can't cope with that much stupidity.
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