Since Sulfamic acids solubility in EtOH is low you can be sure any clear solution you collected was indeed converted. If you reduced volume by 1/2 and used say 2x molar excess of EtOH then it will kind of solidify simular to the way "hot ice" does. I have seen it liquid and cold and as soon as I pick the flask up and swirl it then entire thing solidifys. The long needle crystals are that slush your seeing but they are fragile and break when you shake the flask.

Yeh I wouldn't worry to much about a recrystalization since its a typical solvolysis reaction where the reactant is reacting with the solvent as it goes into solution. Trying to clean up the crystals may cause hydrolysis if ones not careful and just introduce impuritys that where not present.

I have to ask, what is the next step?

After sitting outside for a couple minutes, the entire mix liquefies.
Either, the methyl sulfamate is melting or its solubility in MIBK is significant at warmer temperatures
Upon moderate indoor cooling, a majority of the melt solidifies, but there is still significant liquid in the mix, probably the less volatile MIBK.

What a waste of time
A rerun with dried everclear will follow most likely next week.

Mhm, yeah, that was me. Ammonia and nitrous acid form, predictably, ammonium nitrite, which decomposes to release nitrogen gas above 60 C. This shouldn't be too surprising when you consider that ammonia is basically just annother amine, which, in theory, reacts in the usual way with nitrous acid to generate nitrogen gas, only with the intermediate diazonium ion being HN2+, which is incredibly unstable and will quickly generate a lot of N2. Here's a relevant thread:

http://www.sciencemadness.org/talk/viewthread.php?tid=11958

The following explosive properties of NH4NO2 were detd.: working capacity in a Pb bomb, 350 cc. (as compared with that of trinitrophenylmethylnitramine, 390 cc.), detonation velocity 5250-300 and 7640-840 m./sec. at a d. of 1.04 and 1.45 g./cc., resp., and heat of explosion (H2O as vapor) 54 kcal./mole.

Combining ammonium salts and nitrites is one thing I wouldn't fuck with.

Your ammonium alkylsulfate can probably be converted to sodium alkylsulfate one way or another, and then used safely in the synthesis. Still looks a lot better than any previous route to nitroethane I've seen.

They must be hygroscopic? and absorbing water, and slowly dissolving. Something other things will do - It doesn't seem to me that this should be anymore hygroscopic than ammonium bisulfate though?

Perhaps you ought to pull a vacuum on them and warm them up to dry it a bit. An aspirator can boil water so I'd imagine if you placed the crystals in a flask under a vacuum and than placed that in a hot water bath - they would dry nicely.  

if you dont dry in between, how do you use it in future reactions?
assume 100% conversion?

itd be easier if I just had a vacuum. . .
but what is the process for converting the ethyl sulfamate to sodium ethylsuflate?
i wouldnt want to risk the explosion error

ethyl sulfamate doesn't exist, does it? I thought it rearranged or formed into ammonium ethyl sulfate.
When methanol is reacted with sulfamic acid,  ammonium methyl sulfate forms, and upon its thermal decomposition/rearangment it methylamine*bisulfate. This doesn't work with ethyl alcohol, as it is released as ethylene and leaves behind the ammonium bisulfate

The idea is that once we have ammonium ethyl sulfate - there might be a way to react that with something to get it to produce Ethyl amine, or nitroethane. No one is sure how exactly.

if you want to turn the Ammonium Ethyl Sulfate (AES) into Sodium Ethyl Sulfate, you can react it with a sodium base, preferably something that will NOT release water.. Perhaps (though a bad option due to costs..) Sodium ethoxide..

NH4(Et)SO4 + NaOEt => NH3 + EtOH + NaEtSO4

Vogelzang - 28-6-2009 at 04:37

Alcoholysis of sulfamic acid produces ammonium akyl sulfates. On page 629 of the attached article it discusses an example where methanol refluxed with sulfamic acid for several hours yields ammonium methyl sulfate. Ammonium methyl sulfate rearranges at high temperature to methylamine sulfate.

See ammonium.methyl.sulfate.pdf here
http://psychedelichosting.info/Ionium/Rhodium/pdf
or http://80.244.243.200/archive/rhodium/pdf/index.html



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-- http://www.sciencemadness.org/talk/viewthread.php?action=printable&fid=10&tid=1261

Adding Ammonium Ethyl Sulfate to water would form Ammonium Bisulfate  and release ethanol.

Not to sure what is going on in this thread anymore - I need to re-read it.

trisodium phosphate would be a strong enough base to liberate ammonia in that reaction,
pKa of ammonium: 9.24
pKa of hydrogen phosphate: 12.35
pKa of dihydrogen phosphate: 7.198

this shows that in the reaction with ammonium ethyl sulfate would liberate ammonia gas, and form sodium ethylsulfate and ONLY (except trace amounts) disodium phosphate.
now, the issue would be separation.
does anybody have the solubility data of trisodium phosphate, disodium phosphate, and sodium ethyl sulfate in ethanol?
I'm gonna go check up on those figures now

As to the utility of the ethyl tosylate, I've requested some articles which should shed some light on the utility of the same. Trialkyl Orthoformates are able to be prepared easily enough (ala Orgsyn, I'd try DRY NaOH/EtOH, the bulk of which is in the Alkoxide form according to Nicodem). Klute had a good thread on the tosylate as an alkylating agent @ SM where a paper is given for the transesterification of the orthoformate with toluenesulfonic acid. It all comes down to the hardness or otherwise of the alkylating agent & the solubility of NaNO2 (then again - lithium carbonate is cheap enough to warrant purchasing it - pottery supplies).