Author Topic: NITROETHANE SYNTH, given by Anon  (Read 1778 times)

Sedit

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Re: NITROETHANE SYNTH, given by Anon
« Reply #40 on: December 23, 2010, 04:29:26 AM »
Try making Ammonia Ethylsulfate thru the use of Sulfamic acid solvalysis in Absolute EtOH. The results could quite possibly be used as a direct replacement in the nitroethane synthesis or added to NaOH to form Sodium ethylsulfate.

Added note performing the solvalysis in MeOH forms Ammonia Methylsulfate which undergoes thermal rearrangement to MeNH2HSO4.... Sadly the Ethylvariation does not behave the same way leaving Ethylamine out of the question.


PS: You know what? I realize Im going to have to be the one to fucking to do it even though I have no time nor money im going to have to be the one to perform the simple AES experiment and see if Nitroethane is produces as it does with sodium ethylsulfate... And yall know what? I might not tell a god damn one of yall except stochastic because I can see hes atlest trying. Hows them books comming along EVERYONE else!
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Re: NITROETHANE SYNTH, given by Anon
« Reply #41 on: December 23, 2010, 08:44:54 AM »
i think there could be some catalysis employed to speed up reaction. never heard of this possibility anyway, thanks!
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Re: NITROETHANE SYNTH, given by Anon
« Reply #42 on: January 08, 2011, 08:21:15 PM »
I would like to hear some takes on conversion of Ethene, I have some ideas that I will discuss later but I don't want to stear the topic into something I already know. Im just trying to consider various means of nitrating Ethene to yeild Nitroethane.
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redcat

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Re: NITROETHANE SYNTH, given by Anon
« Reply #43 on: March 07, 2011, 10:38:43 PM »
sedit, if you havent tried your AES method yet, I'll give it a go.

I think that neutralization would be more effective with sodium bicarb rather than carb

what do you think?

Vesp

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Re: NITROETHANE SYNTH, given by Anon
« Reply #44 on: March 07, 2011, 11:01:17 PM »
redcat, I would love to see results if you do the AES method, and also why do you think bicarbonate would be better than carbonate?
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Re: NITROETHANE SYNTH, given by Anon
« Reply #45 on: March 08, 2011, 02:29:49 AM »
carbonate is a better base than bicarbonate, so I'd imagine unless you added the exact stoich amounts of carbonate, youd partially protonate the carb and bicarb.
I would imagine its a possibility for you to be left with some bicarb left in the mix, leading to an annoying impurity.
If this could be fixed with a crystallization, you would still compromise yields. Judging by the already dismally low yield for the amount of volume ethanol used, I'd prefer to avoid this step altogether.

Using sodium bicarbonate would allow ONLY bicarb to be protonated and gassed out.

Correct me if I'm wrong, but this seems like a better option to me.

atara

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Re: NITROETHANE SYNTH, given by Anon
« Reply #46 on: March 08, 2011, 06:13:09 PM »
Added note performing the solvalysis in MeOH forms Ammonia Methylsulfate which undergoes thermal rearrangement to MeNH2HSO4.... Sadly the Ethylvariation does not behave the same way leaving Ethylamine out of the question.
I would call this a good thing. Ethylamine is easy (hydrolysis of theanine or decarboxylation of alanine), and less chance of thermal rearrangement means higher yields of sweet nitroethane.

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Re: NITROETHANE SYNTH, given by Anon
« Reply #47 on: March 10, 2011, 05:43:55 AM »
No, not what I mean atara, I would welcome if the Ammonia Ethylsulfate would undergo thermal rearrangment to Ethylamine Bisulfate like the Ammonia Methyl sulfate does when converting to Methylamine Bisulfate but instead it produces Ethene and Ammonia sulfate IIRC due to instability issues during the rearrangment. Ethene isn't something to shake a stick at but Ethylamine may possibly be turned into Nitroethane using Oxone oxidations as well as a few others.
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Re: NITROETHANE SYNTH, given by Anon
« Reply #48 on: March 10, 2011, 09:10:03 PM »
I wonder if the ammonium alkylsulfate can be converted to sodium alkylsulfate via reaction with sodium cyanate.

The idea is, ammonia + cyanate --> urea, which is irreversible. The sodium ethylsulfate is stabler than ammonium ethylsulfate and also you avoid the explosion risk of combining ammonium salts and nitrous acid.

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Re: NITROETHANE SYNTH, given by Anon
« Reply #49 on: March 10, 2011, 09:58:03 PM »
Good thinking, I bet that would work just fine. I don't see sodium ethyl sulfate reacting with urea, but it may - I know urea has a tendency to act a bit strange. other sodium salts would probably work just as well, I don't see why they would not? Such as chlorides, hydroxides, or carbonates?
Might have hydrolysis issues - is that an issue with sodium ethyl sulfate?
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atara

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Re: NITROETHANE SYNTH, given by Anon
« Reply #50 on: March 10, 2011, 11:25:34 PM »
I imagine, since sodium chloride is soluble in ethanol and sodium ethylsulfate is probably insoluble in ethanol, that the use of cyanate to drive the equilibrium might be unnecessary.

You would add NaCl to the rxn mixture and collect the SES precipitate.

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Re: NITROETHANE SYNTH, given by Anon
« Reply #51 on: March 11, 2011, 12:45:13 AM »
I wonder if the ammonium alkylsulfate can be converted to sodium alkylsulfate via reaction with sodium cyanate.

The idea is, ammonia + cyanate --> urea, which is irreversible. The sodium ethylsulfate is stabler than ammonium ethylsulfate and also you avoid the explosion risk of combining ammonium salts and nitrous acid.


I have had a simular idea and I have some Ammonia methylsulfate in solution waiting for a Sodium carbonate addition possibly creating Sodium methylsulfate and Ammonia carbonate. Its just a matter of getting around to it in order to test a few things. Remember the Ammonia ethyl/methyl sulfates are there for the experimenting since all one has to do is reflux Sulfamic acid in the correct alcohol until it all dissolves. On cooling large needles of the desired Alkyl sulfate salt are formed. I suggest it to everyone to produce some to experiment with however you desire. I personally want to run some test with the Ethylsulfate and see if the addition of some form of ammonium salt can be added to the melt to stabilize the rearrangement and form Ethylamine thru this method. That would be a huge breakthru.
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Vesp

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Re: NITROETHANE SYNTH, given by Anon
« Reply #52 on: March 11, 2011, 01:06:30 AM »
NaCl is hardly soluble in ethanol, much more so in methanol but still only a little bit. I would not be surprised if sodium ethyl sulfate were not just as soluble...

Solubility of NaCl (g/100 g solvent)    
water         35.92    
methanol         1.40    
ethanol         0.065


What might really be worth looking into is the possibility of some sort of biological process turning ammonium ethyl sulfate into ethylamine?
I know certain materials when they decompose do release NH3, and likely even alkyl amines (what causes the smell of rot for fish?) - so perhaps those same mechanisms could release the ethylamine instead?

It would be really hard to get them to willingly give up the carbon and the nitrogen sources.. however!

Just an idea.. life forms can be inconvenient, but very good chemical factories after all...


« Last Edit: March 11, 2011, 01:14:41 AM by Vesp »
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Re: NITROETHANE SYNTH, given by Anon
« Reply #53 on: March 11, 2011, 01:47:11 AM »
It would be great to see but my knowledge is to limited in that field to even start to decide where to begin when chosing an organism to affect the reaction.

Im leaning more towards the fact that the rearrangment of Ammonia methylsulfate is one simular to a radical reaction but the stability of the intermediat with longer alkyl chains causes the alkene to be released instead. With that in mind I know there are ways of Nitrating or Aminating alkenes meaning I feel somewhere in there lies the possibility of directly converting the Ethene released into Ethylamine or Nitroethane but I have alot more study to do on this relatively unresearched unpublished reaction before I can make a hypothesis on how to go about releasing Nitroethane on the rearrangment phase instead of Ethene.
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Re: NITROETHANE SYNTH, given by Anon
« Reply #54 on: March 11, 2011, 04:44:42 AM »
Insomuch as adding NaOH to ammonium ethyl sulfate in ethanol, it's worth noting that "ammonium hydroxide" is effectively ammonia water, and sodium ethyl sulfate is soluble in water.  While some (if not most) may crash out I believe it may be necessary to evaporate the solution to recover the entire yield.

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Re: NITROETHANE SYNTH, given by Anon
« Reply #55 on: March 11, 2011, 05:01:17 AM »
NaCl is hardly soluble in ethanol, much more so in methanol but still only a little bit. I would not be surprised if sodium ethyl sulfate were not just as soluble...

Solubility of NaCl (g/100 g solvent)    
water         35.92    
methanol         1.40    
ethanol         0.065

Erm. Potassium iodide then, not sodium chloride. Potassium iodide is soluble in all the lower chain alcohols and even acetone, last I checked.

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Re: NITROETHANE SYNTH, given by Anon
« Reply #56 on: March 11, 2011, 01:55:14 PM »
Insomuch as adding NaOH to ammonium ethyl sulfate in ethanol, it's worth noting that "ammonium hydroxide" is effectively ammonia water, and sodium ethyl sulfate is soluble in water.  While some (if not most) may crash out I believe it may be necessary to evaporate the solution to recover the entire yield.

Ammonia Methylsulfate undergoes hydrolysis rather quickly in H2O hence the reason for my avoidance.
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Re: NITROETHANE SYNTH, given by Anon
« Reply #57 on: March 15, 2011, 07:18:05 PM »
50.08 g sulfamic acid was refluxed for three hours in 200 mL denatured ethanol, until all the solids dissolved.
reflux was maintained for about 30 minutes after total dissolution.
the reaction mixture was gravity filtered, and the filtrate was placed in a freezer for an hour.
no crystals were formed, even with scratching.
the filtrate is currently being boiled down to hopefully yield some crystals

is there any obvious error with my procedure?

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Re: NITROETHANE SYNTH, given by Anon
« Reply #58 on: March 15, 2011, 07:27:11 PM »
No idea as I have never done it, you will have to wait till sedit replies.. but perhaps a small addition of H2SO4 would help get the ball rolling?

That is unfortunate it did not work with the ethanol. I believe it has been confirmed to work using that trick with methanol - but perhaps not?
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Re: NITROETHANE SYNTH, given by Anon
« Reply #59 on: March 15, 2011, 08:31:14 PM »
update:
the filtrate was boiled down to about a quarter of the initial volume, and a bountiful white sludge precipitate formed.
completely unlike the long needles described.
they will be dried, and recrystallized soon.
anybody have an idea on a good solvent for recrystallization?
I'd assume ethanol would work, but there may be a better one.
also, i'd like to do a melting point test to be sure the conversion took place
the sulfamic acid melted around 210 C.