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pseudonitrosites via Toennies method

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Antibody2:
Antibody decided to have a dream of using Toennies method of producing pseudonitrosites in using GAA as a solvent. It  was likely a successful dream but being unfamiliar with nitropropenes cannot say for certain.

After expereiencing a particularily fierce mind explosion antibopdy was cast into a deep coma,  and had this dream.

20ml asarone was added to 200ml GAA, asarone takes a couple of moments to go into solution. Meanwhile a 100ml of saturated aqueous NaNO2 solution is prepared.

With no stirring or cooling the NaNO2 solution is dripped into the Asarone/GAA over the course of three hours. Each drop of NaNO2 solution seemed to produce an initial precipitate that is almost immediately disolved.

At the end of addition a viscous bright yellow layer begins to appear on top. antibody initially thought that this was simply the asarone being forced out of solution by the Aqueous  NaNO2, however this layer was considerably brighter than the asarone which had only the faintest traces of light yellow to it. So maybe it is a layer of monomer forming (maybe was greenish but antibody is colour blind so cannot say for certain)

It was left overnight and in the morning the yellow layer was even larger. so the entire rxn was tossed into a sep funnel and left to separate. That evening antibody goes back, and the entire solution has turned BRIGHT PURPLE! two phase cloudy light purple on bottom, and the top layer is deep bluberry, and is so viscous that it clogs the sep funnel. It is partially crystalized. This seems promising.

200ml of 8% KOH in ethanol is added to sep funnel and shaken alot. It goes into solution mostly still some solids at bottom, so heavy mag stirring is attempted to bust them up.
This results in the stuff that had been in solution all of a sudden sticking togather in an yellowish white blob of gum. This is hell to break up. Try crushing with spoon and with herculean manual shaking. Finally most of it busts up. and solution is very cloudy and dirty yellow/orange with just a couple gobs of gum on bottom.

This is chilled in freezer for half hour (no ice) then mixed in a big erlynmeyer flask with 1l of 3n HCl, initially there is alot of off white/yellowish precipitate that fell out, but after heavy shaking all the precipitate floated to the top, it is bucknered and washed with water and dilute HCL, then left to air dry,

After is is dry the crystals are weighed 16.4g they are very crunchy with the majority being yellowish off white kinda colour, but the chunks of gum that never broke up when those are crushed there is Bright orange crytals inside, much more crystaline than the rest, they comprise maybe 15% of the total.

Antibody is not sure what he has is in fact nitropropene, any opinions?

Antibody is not sure if sodium acetate was produced and crystallized and what would happen to it when placed in the alkaline alcohlic solution, or if potassium hyponitrite was produced. Antibody thinks one or the other of the crystals is nitropropene. and the rest is something out.

Antibody has been dreaming these pseudonitrosites for awhile now, and would greatly appreciate the opinion of a more enlightened dream interpreter the himself.

antibody thinks he has given a pretty detailed account and hopes it will be eneough for some bee to tell em if heis dreaming in the right direction.

Found the purple colour very perplexing, any thought on that? it disappeared immediately on going into KOH solution?

Jimi loves ya!

CHEM_GUY:
What is the reference to Tonneies method?

The purple is very perplexing...  Maybe there was some acetyl substitution as well.  I thought that asorone-pseudonitrosite was bright yellow...   Maybe the dimer-pseudonitrosite disassociated in the acetic acid and formed the monomer which is intensly colored and a blue/green...

Since the preceptiate from the KOH hydrolysis is a yellow I imagine that there was at least some nitro-alkene formed. 

Try hydrogenation and a bioassay and tell me how goes it...  Good work.  By the way, please if there is a reference for this varition please private message me it.

Read my Disclaimer:  http://cantsueme.homestead.com

obituary:
swim would also like to see this other variation if it is available/exists.  and also, question for antibody- why your choice of solvents?   reasoning?  (just curious)

Maighstir:
Also very interrested.


Vae victis meretrix est et mors venit.

Maighstir:
Just did a pseudonitrosite experiment with hexane as solvent. I didn't finish it but maybe it helps.

I started to experiment with 30 ml of star anise oil (medium quality) and decided to practice without distilling. I poured the oil in about 200 ml of n-hexane in a 1L (what the hell do you call it in english) erlenmeyer (you know, the one with the sidepipe for filtration with a Buchnerfilter). Next I prepared a solution of NaNO2 by dissolving 80 g in d.water. I put about 150 ml of 20% H2SO4 in a sepfunnel (using this as a drippingdevice), added the oil/hexane to the NaNO2 sol. and put the sepfunnel through a stopper and onto the erlenmeyer. I connected a rubber hose to the side of the erlenmeyer to lead NO2 gas outside. The sepfunnel was set to drip the H2SO4 to the mixture over the course of 6 h (without stirring). Almost immediatly some amber colored goo formed at the interface of the water/hexane and brown gas escaped. Obviously my cork stopper didn't function properly because the place started to smell. After a few hours there were dangerous amounts of NO2 gas in my little lab and without breathing I opened everything and put in a fan. Twelve hours later I returned to find that the smell had gone and the amount of amber goo at the interface was huge (I started with 30 ml of oil and there seemed to be almost as much goo). Next I sucked the hexane and the water off using a vacuummech. and a glass tube. I placed the flask in a boiling water bath and after a few minutes the goo started to bubble and turned dark brown (again some brown vapour escaped). While hot I added some 96% ethanol and immediatly white cristals precipitated out of solution (everything went according to the article). I didn't continue the experiment yet and if I had to guess, I'd say there was about 6 to 7 grams of pseudonitrosite. I know it's not much yet but it's only a first time test. I'll continue this later and more accurate.

Hope this is of any help,

Maighstir.

Vae victis meretrix est et mors venit.

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