Antibody2 (Hive Bee)
08-04-00 21:53
No 36661
      pseudonitrosites via Toennies method  Bookmark   

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
(Hive Bee)
08-05-00 00:30
No 36706
      Re: pseudonitrosites via Toennies method  Bookmark   

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
(Hive Bee)
08-05-00 02:11
No 36739
      Re: pseudonitrosites via Toennies method  Bookmark   

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
(Newbee)
08-05-00 09:58
No 36935
      Re: pseudonitrosites via Toennies method  Bookmark   

Also very interrested.



Vae victis meretrix est et mors venit.
 
 
 
 
    Maighstir
(Newbee)
08-05-00 10:30
No 36947
      Re: pseudonitrosites via Toennies method  Bookmark   

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.
 
 
 
 
    obituary
(Hive Bee)
08-06-00 21:25
No 37339
      Re: pseudonitrosites via Toennies method  Bookmark   

>a 1L (what the hell do you call it in english) erlenmeyer  >(you know, the one with the sidepipe for filtration with a >Buchnerfilter)
vacuum (filter) flask
erlenmeyer w/vacuum side arm attachment

the star anise oil that you used, was it straight oil, or just asarone?  in other words, purified or crude?

swim was unaware that asarone was a component of star anise oil.  he knew anethole was a component though.  confusion?
 
 
 
 
    Penis_Seinfeld
(Hive Bee)
08-07-00 02:57
No 37454
      Re: pseudonitrosites via Toennies method  Bookmark   

Oh boy, I actually get to post in the novel forum.

Most propenylbenzenes can form pseudonitrosites.   There is no asarone in star anise oil, but both asarone and anethole are propenylbenzenes.


PS
--
Chairman of the IAADCMSWMC and President of the MH Society
 
 
 
 
    foxy2
(Hive Bee)
08-07-00 12:10
No 37733
      Re: pseudonitrosites via Toennies method  Bookmark   

Your results sound similar to my buddys except he didn't let the rxn run long enough.


"Vote Libertarian"
 
 
 
 
    Antibody2
(Hive Bee)
08-08-00 02:17
No 37922
      Re: pseudonitrosites via Toennies method  Bookmark   

CHEM-GUY - the only reference was the half of a sentence that appeared in Rhodiumís faq on pseudonitrosites. Antibody figured ratios couldnít vary that much, and so what if there is excess GAA, its the solvent as well as a reagent.

Antibody has the bruckner refs and there are no refs to toennies there either perhaps they will be found in one of the other refs on Rhodiums faq.

In the bruckner refs there is tons of talk about acetoxy derivatives, but unfortunately antibody canít read German and is having one HELL of a time trying to get the fucking things translated. Antibody feels like poking his eyes out over this one! Anyone who would like to help antibody translate gets a big kiss.

Obituary - Antibody dreamed this dreams becuase dreams using pet ether was were resulting in tar and havenít got around to dreaming up any diethyl ether yet, but have lots of GAA in dreamworld.

Maighstir-try running a hose off the sidearm of the flask out a window

Unfortunately hydrogenation was a total loss, a kink in the condenser hose allowed the rxn to boil dry while antibody was dreaming of 9-5.

Perhaps the pseudonitrosite is slightly soluble in the GAA giving the blue-green color, which it might be because antibody is pretty much color blind a so cannot see green.

Will dream again but will try to isolate yellow layer while still yellow or part of it anyway and do a comparison.



Jimi loves ya!
 
 
 
 
    CHEM_GUY
(Hive Bee)
08-08-00 03:26
No 37954
      Re: pseudonitrosites via Toennies method  Bookmark   

Just post the German and ask someone to translate.  Rhodium reads german as well as many others...

I posted something in german a while back and somebody translated it for me, so maybe the same will happen this time.


Read my Disclaimer:  http://cantsueme.homestead.com
 
 
 
 
    obituary
(Hive Bee)
08-09-00 08:35
No 38514
      Re: pseudonitrosites via Toennies method  Bookmark   

so the basis of the propenylbenzenes all being applicable to the pseudonitrosite synths is that they all have the double bond between carbons on the chain (with high reactivity)  allowing for two additions of NOx (NO and NO2)on the chain?  this further allowing for the dimerization of two molecules? 

if the decompostition on storage of pseudonitrosites is present at 40*C (essentially a low heat decomposition, less thermally stable at elevated temps), could the dissociated dimer be broken down into NOx gas and the monomer by heating in a high bp solvent by evolution of the gas therefore driving the equation to the right? (maybe a catalyst needed for breaking the N bonds)
 
 
 
 
    uemura
(Stranger)
08-14-00 16:00
No 40740
      Re: pseudonitrosites via Toennies method  Bookmark   

Uemura wants to add some infos to the pseudo nitrosite of the Anethol. There is a extensive article from Wieland, 'Zur kenntnis der Pseudonitrosite' (on the knowledge of pseudo nitrosite), appeared in Annal. d. Chemie, 1903, Bd 329. Wieland cites Toennis but mentions that Toennis does not give experimental or analytical details. Wielands procedure is as follows:


To 20 g Anethole in 100ml GAA a saturated NaNO2 solution is slowly added under cooling with ice. The original light green color turns to yellow during the addition. If the mixture gets cloudy, additional GAA is added.

As soon as the yellow brown color becomes stable, the mixture is kept as it is for some hours. After this time the nitrosite precipitates in fine needles. They are filtered, washed with GAA and several times with ether. From the mother liquid often another small amout cristallises after some time. The total yield is however rarly more than 15% with respect to the anethol.
The nitrosite can also be obtained by saturation of a concentrated solution of anethol in ether under strong cooling. The purity of the product is high in both methods. The nitrosite decomposes at 120DegC, depending on the heating.

Wieland also describes how to get the nitroanethol.

In 20ml 10% KOH in EtOH 3 g Nitrosite is added slowly under moderate cooling and heavy shaking. The nitrosite solves immediately without development of gases. The mixture is diluted with water such that the solution does not get cloudy. Under ice cooling the mixture is carefully made acid. After a short time, the beta-nitroanethol appears as fine yellow needles. If it appears as oil, adding a single cristal is enough to get it as a solid. Yield is about 80-90%. melting point is 48DegC, re-cristallisation from diluted MeOH.  


"I want to know God's thoughts, the rest are details."  A. Einstein

 
 
 
 
 
    CHEM_GUY
(Hive Bee)
08-14-00 17:38
No 40758
      Re: pseudonitrosites via Toennies method  Bookmark   

Thank you very much!  A great post to say the least. 

15% isn't that great, but the purity is good. 


Read my Disclaimer:  http://cantsueme.homestead.com
 
 
 
 
    uemura
(Stranger)
08-15-00 19:35
No 41236
      Re: pseudonitrosites via Toennies method  Bookmark   

Uemura did some homework and went thru the last section of the Wieland paper mentioned in his previous post. At the very end of the paper, he found a very interesting thingy, worth top be posted. Here it goes:

Anismethylglyoximperoxid or
  
CH3O-Benz---C--C--CH3
                    "  "            <- should be double bound (sorry for the simplistic ASCII representation)
                   N  N
                   |  |
                  O--O
           
is the MAIN PRODUCT of the reaction of anethol and NaNO2-GAA!!!!

Uemura is not smart enough to extrapolate this statement to other propenylbenzens (like asorone) but he wants to put this for further discussion. The more or less correct translation of the resp. para is like this:

This compound (the above one) has been discovered by Toennies and has been identified uniquely by Boeris, a scholar of Angelis as Glyoximperoxid. [Gazz.chim.23,II,165] It should be mentioned that in any case this compound is the main product in the reaction of Natrium nitrite and glacial acetic acid.
The best method for preparation is the one given for pseudo nitrosite, however without any cooling. Under these conditions the mixture cristallises after short standing to a dense mass of long needles. Re-cristallised from EtOH a mp of 97DegC and all other features reported (BY WHOM??) are found. yield almost 100%. Pseudo nitrosite cannot be produced in this way. The peroxid goes? with water steam, is solves in conc. sulphiric acid with orange color. The color disappears when water is added, the peroxid is recovered unchanced.

And another point:
the amphi-dioxim of the anismethyl-1,2-diketons is produced when the above GAA-NaNO2 mixture is heated to 50-60DegC.  (Uemura ignores the ASCII display)

O.K. bees, Uemura learns the following:

All the NaNO2 - acid treatments of propenylbenzens are very sensitive to temperature and other parameters.
Anyway, we knew that before but now we have further confidence. Uemura also agrees with Osmium that the solvent is only one of these params.

"I want to know God's thoughts, the rest are details."  A. Einstein
 
 
 
 
    Antibody2
(Hive Bee)
08-16-00 16:10
No 41564
      Re: pseudonitrosites via Toennies method  Bookmark   

uemura-hats off to you bee, you seem to dig these refs up at a prolific rate.

Antibody got into a car crash and was lost to a coma, while in coma he dreamed the same dream he had at the top of this thread except he used out of the bottle calamus oil.

When all the NaNO2 solution had been dripped in a darker layer (not orange because used raw oil) finally formed on top. Not waiting for it to turn purple or crystallize this time it was separated, and tossed into the 8% KOH followed by ice and dilute HCl. This time there were no crystals but a dark oil settled out on bottom (maybe should have waited for it to turn purple and crystallize).

Antibody remembers reading in TSII that nitropropenes produced in GAA sometimes yields an oil. Anyways recrystallization was attempted but resulted in more dark oil.

Hydrogenation attempt to follow, will keep bees posted.


Maighstir - Have been pondering the use of Hexane, interesting that your goo was orange and not the black/red tar everyone else seemes to be coming up with.



Jimi loves ya!
 
 
 
 
    Maighstir
(Newbee)
08-19-00 11:18
No 42741
      Re: pseudonitrosites via Toennies method  Bookmark   

Antibody> I did have a hose attached to the side-arm but it was not sufficient enough. I did some more testruns with hexane (on an DCM extract of celery>>>filtered only once) and again no tar. Hexane seems to work OK.

Right now I'm waiting for some oils to be delivered. When they do I'm gonna do some more serious work.

Maybe later,

Maighstir.


Vae victis meretrix est et mors venit.
 
 
 
 
    Maighstir
(Newbee)
08-19-00 12:52
No 42762
      Re: pseudonitrosites via Toennies method  Bookmark   

Please sent me the german article(s) and I'll translate them for you (no prob).

Sent to Meriadorc@hotmail.com

Later,

Maighstir.


Vae victis meretrix est et mors venit.