This prep suggests that under mild conditions, utilizing a 0.05M dimethyldioxirane solution removed from light and reacted in accordance to this paper, that under such condition it is possible to convert primary, secondary and tertiary butylamines into nitro derivatives in 80 - 95% yields.
This paper also includes the successful oxidation and nitration of aniline, cyclohexamine, and somewhat goes against what is generally believed and is often accepted about the formation, and in particular the formation of primary and secondary nitro alkanes, as not viable for such species. I am not sure if indeed this paper is peer reviewed, I have not gave any of the cited references a check for collaboration, but with this said, it is of interest, and could somewhat be used in the potential formation of the oxidation and nitration of alanine, followed by decarboxylation, by mineral acid, in order to present this much sought after superior RC FUEL additive and useful in various aldol condensation reactions being Nitroethane.. The paper also present the likelihood that under these same conditions it may well be of interest in successful generation of nitroparafinss from lower carbon chain derivatives.

The reagent known as dimethyldioxirane, is likely to have to be prepared, and distilled, in order to obtain a working concentration.. I am not totally clear on this reagent, as initial I was led to believe a buffered acetone mix that included oxone would serve such purposes, yet will be clarifying this, and will present the procedure that will enable selective oxidation and formation of nitroderivaties from various amines..

Just in case there is an interest in that paper, using oxone, well I found that if one adds oxone to water, and brings the temperature down then no precipitate occurs at 2 deg, but if one lets it get to freezing, and then takes it out and brings the temp up, the precipitate occurs.. So far I have done this 3 times. Removing solid, adding more oxone, and repeating that procedure, and taking out much less salt than just adding each time.
I will then add this in 2 ways to acetone and see if this paper can be somewhat worked

The attached paper is another earlier use and generation of DMDO and may be of interest if anyone also sees potential in oxidizing amines etc.

Anyone with the time & effort (not to mention the interest) might want to go through WD and find a post by Java (in reply to a request for a reference by loose_e IIRC) which dealt with the prep of nitroethane using a column and ethyl halide (thus avoiding the solubility issues). Here is "A" reference to the basic procedure (see page 16/60):

Nitroallmnes labeled with carbon-11 can be easily prepared by reacting the appropriate [1lC]alkyl iodide with silver nitrite at 80°C.
This approach is amenable to on-line processing where the purified [llC]alkyliodide is flowed in a nitrogen or helium stream through a 3 mm id x 4 cm length soda glass column packed with 0.4 g of silver nitrite at 20-30 mL/min. (Schoeps et al., 1989). Radiochemical yields (based on 11C02) of 55Y0, 30V0 and 40% are typical for preparing [~*C]nitromethane, [llC]nitroethane and [llC]nitropropane, respectively.

Obviously the various papers by Schoeps, et al may well be instructive



As an aside, isn't a nitrite just a salt of nitrous acid? Such as would be the output of the electroroutes (@ SM) prior to oxidation of it to nitric would it not? So if we formed the salt (carefully - using minimal calcium carbonate) then form sodium nitrite from that using sodium sulfate and filtering the precipitated calcium sulfate.

Depending upon where you are and what the laws are probably... It is a listed precursor most places and "prove-able" intention to make a listed precursor would be a bad thing, if however you were merely trying to make ethyl nitrite and it came across as a by-product....

You will not produce Ethylnitrite you will produce Nitroethane the isomer of Ethylnitrite. Ethylnitrite is an ester of Nitros acid with ethanol and is very volitile. I have only run the synthesis using MeOH to produce Ammonia methylsulfate which will isomerize to methylamine bisulfate at high temperatures. It does not work with the Ethyl equivalent thought .

However you will still get Ammonia ethylsulfate from the solvolysis of Sulfamic acid in EtOH and once dried that should act just like Sodium ethylsulfate and I have a good feeling that the ease that ammonia normaly dissasociates means we may just see better results using AES instead of Sodium ethylsulfate.

The Yellow discoloration was present when I performed my Ammonia methylsulfate synthesis but I assumed this was impuritys in the reaction and UC over at Science Madness produced a clear post reaction fluid that on cooling precipitated long needle like crystals. I on the other hand just switched right over to distillation and removed the remainder of the alcohol at while point when the alcohol stopped comming over it crystalized simular to the hot ice experiments on youtube.

I think one should ensure that all EtOH is removed prior to running the experiment with the nitrite just to be on the safe side since any excess EtOH will form Ethylnitrite and you don't want that since it has a low boiling point and will give you a head ache if you breath to much of it.


Anyone have any idea of why the chose to use a Potassium carbonate instead of sodium carbonate in this reaction BTW?

I posted the prep in a few post earlier and yes they must be mixed as well as possible for best results from what I understand.

BTW when your stirring stopped you could have continues the reflux but it takes about twice as long to dissolve. I never used stirring when performing the experiment with AMS and it took about 6 hours for a little over half a mol IIRC..

I do have a quick question that about something I forgot to mention. ... Was your EtOH anhydrous?

Sulfamic acid undergoes hydrolysis with hot H₂O. If there is water in the reaction it will more then likely fail. One is suppose to incorperate a drying tube when performing the synthesis.  :'(

Yeh I forgot all about mentioning it befor so Im glad you dried it first or I would have felt bad.

Ok so mez after 2 yrs decided to give this thing a try, and it was one disaster after another. Now don’t jump to conclusions about this synth just yet, because you see when it comes down to a mez orientated disaster, such a result is “not” necessarily indicative of the synth currently up for discussion but more in tune with the experimenter’s own inadequacies due lack of formalized experience or education.  However there is one good thing going in his favor when he approaches these synths and that is after a decade state sponsored sojourn where he quickly understood the meaning of “Yessum I reckon I can falla orders to a capital T otherwise I can kiss my white ass goodbye” otherwise the best you could hope for was maybe a trip to the infirmary prior to hole time, oh and don’t forget they now charge ya for the bullet they put in your ass. Point is unless I missed something out of ignorance, I am the last person who will begin making changes where there shouldn’t be any and I am the first to admit it. So input would be much appreciated as one has already lost close to 2l of etoh from his own stupidity.  More on that in a minute.

One had observed through much reading that there still was a lot of questions over this synth including mysterious sludge, mine where amongst them a few years back and some of the older bees over at WD tried to help, but guess what… still confused however almost 7 yrs had gone into preparing for this moment (yes the math may bee confusing but think about it, you’ll get it) and was not going to let something like not understanding exact ratios. Before you make jokes I am well aware of what a ratio is, however not sure how it applied here but no matter, it seems that the org. synth. according to most was way too conservative on their etoh mandates and more than a few suggested going much higher. How much higher?  Ha, more of that in a minute).

Ok, so NaHSO was weighed out literally as 113 grams in spite of whatever parts was supposed to imply(now if it happens to mean actual grams as well then that was pure luck).  As for etoh that is a separate story, initially tried really hard to picture what 20 parts by weight of etoh looked like, however talk about confusing.  Are we talking about parts per weight of NaHSo literally, or per mol weights of NaHSo or the reverse which would be either but for the etoh also is there a conversion that needed to be done such as ml to gr? Then one kept hearing iirc...Nicodem’s voice in one of the nitro threads at scimad about the need of additional etoh.  So mez sez  “the hell with it, whats a little extra etoh, after all just spent 2 days distilling a grip and had roughly 2.5l.  But how much was the next question, so one kinda figured out a rough estimate by applying the ol’ lighter fluid trick from the days of yester year's HI reductions (though in concept totally unrelated).  However with the verdict still out on precisely the right amount, I just eyeballed the NaHSO and 2x with etoh, let her come to a boil then waited, and waited, and waited.  

Nothing seemed to have happened... Ok, so mez is also sometimes guilty of breezing thru the smaller details in a synth or even worse mis-interpreting them to mean something else.  According to mez at this point the original stated to be on the lookout for the NaHSO to literally disappear (no I don’t mean magic trick but dissolve), so he was set on this and had not paid heed to what was actually stated which at the current time means the disappearance of the actual NaHSO crystal formation which by no means means total dissolution of product (boy your good if you followed that one).  Well, he was fed up at that point and tossed the whole thing. ..

12 hrs later decided to run it again, this time with a few minor modifications (in the setup only) accompanied by the resolve (3 days no sleep) to see it thru, and a grip of materials depending on this thing to work out otherwise they are just wasted (more on that at the end).  This time the run was 2x the original synth with almost 4 times the volume of etoh by eyesight.  A reflux apparatus what attached to a triple neck 2l since he really didn’t like the idea of losing all this etoh through evap with no idea as to the adequate amount of time to let it run but in his head the reflux condenser should help minimize etoh loss should this bee a lengthy ordeal.  Also since during the prior run it was observed there was no positive signs in regards to visual or smell, and I wasn’t about to taste it, and no time had been stated in either the patent or in E.L’s version, it was decided to let her run for appx 60 min. At the expiration of this time it was observed that the etoh was still relatively the same color as it was during the outset, and although there was a marked decrease in the crystalline structure of NaHSO, one was still not in possession of the “infamous” sludge, though in hindsight it may have to do with his “conservative” amount of etoh .  The ph part seemed simple enough.  Now mez may have it wrong but he was raised a titrater (?) with a few drops of phenyl red indicator into the dual layer solution containing ma in non-polar (kingston), and aqueous layer (DH2O) in an effort to get her peachy (ma to migrate from non-polar into polar) via addition of hcl, however despite experience with anything other than the aforementioned he thought with reasonable confidence what needed to be achieved.  And for the first time in his history, was in possession of a temp/ph meter via our favorite internet site via china.  So what could go wrong?  

Just prior to neutralizing the solution it was discovered that calibrating the meter was not working.  On this particular model you calibrate at slightly higher than DH20 neutral or “ph perfect” as my ex would say.  F#*%)@ B#)%*…then submerge into borax solution and meter should equalize(?) itself to appropriate ph of that solution.  Well it never did, and I mean by a long shot.  So it was decided to drop her (the meter) into some DH2O out of a fresh jug (to decrease possibility of inaccurate reading due to contaminated water and also having calibrated device to both solutions independently of the other in case of contaminated calibration solution).  Again readings ran sporadic, sometimes into triple digits which he didn’t think was possible then all the way into 1’s and 2’s.  What the heck was he supposed to do except buy American?  Time and money being short I decided to run and grab the old pool ph strips Though very obviously limited just maybe they give shed some light on the progression of things if done slowly enough to come within range.  Nada thing.  The color remains burgundish throughout.  Well, here goes nothing, as he is adding the base he realizes this is much like his favorite childhood pass-time which many older kats frown upon since a simpler way is to be had.  However to mez, this way was much more exciting and didn’t involve strenuous arm excersises such as stirring or shaking.  That would be to get ones non-polar (colmans again) next to boiling while making sure to occasional mix down into aqueous layer containing goodies to promote even heating, then carefully remove  from heat and commence tapping in a steady stream of naoh.  Whoa talk about exciting.  Anyways back on subject.  He proceeded to warm-up the solution just slightly then very much like the old days began tapping in his base (not naoh) noting that changes began to occur immediately, the solution began to darken into the red spectrum.  The color kept dropping deeper and deeper into the red, and the smell which at first was kinda nice (being used to boiling HCL and all) quickly got kinda nauseating.   However one continued onward and this time took the liberty of stirring quite a bit throughout the addition of base.  This part did seems like a reaction because the fizzing and somewhat of a battle seemed to be taking place down in the ol’ beaker.  Gradually the solution began to lighten and this reminded me of trying to get the solution “peachy” minus any ph indicator however, though he may have gotten the intended sodium ethyl sulfate the problem was everything was still in liquid form.  So without a ph tester he took the liberty of interpreting the synths use of “neutralize” to mean, when the acid stops being a bitch and screaming her ass off down there every time you drop in some more sodium carbonate.  You know in his mind it meant “neutralize” her.  Yeah don’t say it I know… anyways at this point that the color of solution started to lighten, in between additions it was observed more and more crystal type structures began to take form in the now thickening solution.  Still I was unsure if this was the gold one should bee looking for or just wet crystal formations of the base.  And still yet the formations were not very strong and didn’t stay solid for long so I kept adding until they did and the hissing stopped. The result was one would observe should they have ever experienced batter used to coat chicken or fish after being used continuously. So into a zippy and then into storage she went until it was figured out what should be my next step. I was looking at the solubilities of both the base and sodium ethyl sulfate, they seem virtually identical at least in this regard, and with wik being incorrect on at least one point when deciding to classify sodium ethyl sulfate in with diethyl sulfide.  Meaning diethyl sulfide which is not soluble in water and sodium carbonate is to a certain point so if their decision to relate ethyl sulfate as the same as diethyl sulfide then separation should be a snap with one proceeding by pouring the whole mess in a very liberal amount of DH2O. However the reality is unlike diethyl sulfide, sodium ethyl sulfate of course is very much soluble water so this method being used for determination seems unlikely.

A few days later it was decided that more etoh needed to be distilled as a friend has over 3 benjamins of methylamine.  This being the product of near quantitative yields and using the hofman method, surely he is wrong since although a possibility it really is never expected when discussed in the literature so he wants to remove any ammonium chloride traces that could exist and get a better assessment.  It was at this point decided for whatever reason to combine the recycled etoh used in the sodium ethyl synth with the fresh stuff currently being distilled (aka for me short path distillation = pre-drying to remove unnecessary volume) and then on to the actual addition of drying agent.  However on accident (3 more days no sleep) one may have added naoh instead of the normal drying agent to effect drying.  Well, this wouldn’t have been a catastrophe by no means under normal circumstances since experience has shown the only disappointment is the amount of naoh needed to affect desired results.  However within the first few minutes all of a sudden the solution heating up rather quickly and again took on that deep red color along with that unforgettable smell.  So what gives?  Didn’t bother to try and distill out the red this time nor would have wanted to as this accidental revelation of what was in the etoh made one a bit unnerved about using it again.  One may have to throw in the towel on this one not just due to this new little problem but also as already mentioned the seemingly unmovable hurdle of DMF or the lack of and newer information stating the ineffectiveness of DMSO.  It’s kinda disappointing since a lot went into setting this up properly.  Like catechol, a bit of phloroglucinol via china for variety and its supposed effectiveness as a scavenger in this process (do you know they want close to $200 for 20 grams due to a zone to zone delivery scam), quite a bit of Urea and DMSO and of course no short supply of either Sodium nitrite or Silver nitrate since one was taking no chances, a decent column which should easily give the suggested theoretical plate count, etc, etc.  Yeah you could say it would break thine crystalline heart to see this one fail. Now it looks like only alternative is going into the dark room for 24 after making some “DRY” ether, hey whats ether and can I smoke while I work, it calms the nerves… Just kidding, hey sed remember my flashing acetone experience.  Yeah not so funny however I have learned alot and that includes boiling a pot of met#*%#&@..acetone over a gas burner adjusted to "what the hell were you thinking" is not conducive to maintaining ones product or eyebrows, fuckers.

Anways again though there may not be a lot of experience with this procedure and with DMF taking an exit maybe lesser still in the future.  Any insight is greatly appreciated.

Much love,
Mez

Sorry for reviving a dead thread. evil_lurker's suggestion of using the temperature dependent decahydrate to remove water and make sodium ethyl sulfate does indeed work.

Materials:
113g sodium bisulfate if monohydrate, mp 58.5°C
or
98.4g sodium bisulfate if anhydrous, mp 213C
   + 14.8g water if anhydrous to make monohydrate (sit overnight)

20g grain alcohol
~10g sodium carbonate (add till neutral pH)
Bowl big enough to cover rbf filled with crushed ice/salt water slurry.

Procedure: 15g of water is added to 98.4g of anhydrous sodium bisulfate in a rbf, stirred to a mash, and left overnight. This results in 113g of sodium bisulfate monohydrate that fills the bottom of the flask to a slightly higher level and formed a smooth flat surface.

The monohydrate is crushed and shaken to a flowing granular powder and 20g of ethyl alcohol is added and stirred. A condensor is attached and the flask put into a gently boiling water bath. Very little reflux is observed but the bisulfate monohydrate melts eventually and pools at the bottom. The granules, while previously in piles above liquid level are now below the liquid line in a 1 liter rbf.  The slurry is stirred by hand every few minutes until it melts but thereafter less attention is paid except to break hard sub-surface layers when they form.



The flask is taken directly from the heated water bath and submerged under ice water. The cooling sodium sulfate/ethyl hydrogen sulfate is stirred until the temperature falls to ~22C. There was very little liquid left at that point and it definitely becomes thicker, clumps, and sucks up the liquid at 32C.



The up-ended flask is poured, shaken, and slapped to get as much of the crystal slurry out as possible and onto the filter paper sitting in a funnel. With considerable poking, squeezing, pressing, and agitating of the rapidly solidifying sodium sulfate mass in the filter paper a clear filtrate of some ~20+ ml  (estimated visually) is acquired. Care should be taken to keep everything cool during the filtration.

The excess sodium sulfate and ethyl hydrogen sulfate still sticking to the sides of the rbf  is removed by washing with as little denatured ethyl alchol (no water) as possible. This is poured over the slurry in the filter to help push out the liquid. The resulting liquid is a transparent light yellow.

To the ethyl hydrogen sulfate 1g portions of finely crushed anhydrous sodium carbonate are added, with much fizzing, till pH is neutral. During and after the addition of each portion of the carbonate heavy stirring and manual crushing was required to prevent chunks of sodium carbonate being surrounded by a passivating layer of sodium ethyl sulfate.

When the pH is neutral the remaining liquid, assumed to be ethyl alcohol, filtered out and saved for the next batch.



The remaining wet sodium ethyl sulfate forms a cohesive mass on filter paper when drying. This becomes a very smooth but obviously crystaline flour-like white powder when dry. Results in ~10g sodium ethyl sulfate of questionable purity because there may be some tiny sodium carbonate particles remaining.