Iv been meaning to start a random experiment threed for a little while now but never got around to it. So I thought why not do it now.
As many know almost every experiment I perform is random, Must be ADHD or something

Today I experimented with Fentons reagent which is a powerful oxidizer able to reduce almost all organics to CO2 and H2O and where as I cant give you and quantitive data I just thought Id tell you about some sights, colors, and smells instead.The reason I am trying to get a feel for this is as such,

ALKOXYL RADICALS

Intermolecular substitution in the aromatic series with participation of an RO' radical is observed extremely rarely: it possibly occurs during anodic methoxylation, in which neither MeO" nor MeOH apparently
participate and in the well-known but special (for alkoxyl radicals) case of hydroxyl radicals [generated by
the Fenton reagent (H202/Fe 2+) or H202/hv]. The possibility of methoxylation was shown by Taylor [4] only
in a special case in which the yield of substitution product did not exceed 20%.

Fentons reagent is a mixture of H2O2 and Fe(II) salt. I used Fe(II)sulfate because I had it on hand. First test I tryed was to drip 35% H2O2 on Fe(II)Sulfate to see what happened and I was quite shocked by the results. This is a very violent reaction and I cant stress that enough. As soon as the Peroxide came in contact with the Sulfate it would turn the Fe(II)sulfate blood red and instantly vaporize in a mushroom cloud of steam and vapors. The heat given off in this cloud was amazing if you ask me and you could feel the radiant heat from a little bit away from the mixture. I half expected this mixture to ignite at one point of another but try as I may(and I tryed )I couldnt get it to spontaniously ignite. As exciting as this all was I quickly tired of it and decided to move on to see if I could put any of this to good use.

So I decided to see if it could oxidize MeOH to formaldhyde. I added a small amount of MeOH into a testtube followed with a spatula of Fe(II)sulfate and a few drops of H2SO4 to lower the PH(suppose to be around 3-4 for the fenton reagent). 35% H2O2 was once again slowly driped into the mixture and the green solution quickly turned the blood red color again and this time was way less violent. Fine Bubbles apeared on the bottom and the tube heated up quite abit. Driping with an eye droper was continued for a little while and I decided to take a whiff of the reaction to see if any change had taken place which it did. I was expecting formaldahyde but it smell like it. It smelled more along the lines of ....burnt...formic acid?... I feel that two things should have been done differntly. More time with the addition of H2O2 and an Ice bath to keep the reaction cooled. One very unusual thing that happened was after all was said and done and the mixture cooled I left the mixture and went away for some time. when I came back the reaction had at some point or another flared up and splattered its contents all over the place leaving a pale yellow solution at the bottom of the test tube. The only thin I can think is after all the organics are used up this reaction starts to spead up with nothing to feed on and spews its contents all over in a runaway reaction.

Conclusion: Well not much of anything except the fenton reagent is a beast. Able to oxidize organics down to CO2 and water more work will have to be done to learn to tame this dragon. One thing that I do see use for it is as an emergency destroyall bucket containing an Fe(II) solution with a bottle of H2O2 sitting near by. If that day ever comes and you have time to do something about it dump every thing you want destroyed along with the flask them self, dump in some H2O2 and get the fuck away from it. It will quickly destroy and evidence one may have laying around into nothing. I know people that use to have glassware and stuff laying around thast kept a bucket of bleach just for this reason and when there house was suddenly surrounded by about 20 cars with flashing lights the succeeded in destroying all there glassware and all the precious stuff in it and filling there kitchen with Chlorine gasing them out of the house. Good thing the 5/0 was just there because they where chasing a stolen motor cycle and it crashed out front of this persons house without them knowing...better safe then sorry I guess::sigh::

Fuck Im rambling.... Where was I....

I dunno fuck it....Ill post more random experiments when I feel like it...

Remeber kidz...
Just say no to VD,
~Sedit

Little more screwing around with the Fentons again I tryed to see if I could make some acetic acid by dissolving some Fe(II)sulfate and a little sulfuric acid into ethyl alcohol followed with oxidation thru the addition of H2O2. It worked well I think. It was small scale and yeilds where not found at the moment but after the slow H2O2 addition there was a very faint hint of acetic acid so I very gently heated the mixture for about 30 minutes and after returning the smell of acetic acid was very strong and a small amount of floculant precipitate. It was obvious though that there was EtOH also there so in an attempt to recover the AcOH I added sodium Bicarbonate until fizzing stoped and evaporated the remaining solution.

Very fine slippery needle crystals where obtained and after the addition of H2SO4 the Smell of AcOH was strong.
I almost forgot to mention that after it was neutralized the solution contained another smell that may be of intrest to some. Now instead of smelling like vinegar it smelled like Apples.. There has to have been some Acetaldehyde in there also which I think the precipitate maky have been the trimer of it but im not sure. If someone wanted to make a go at it then possibly recovery of it thru some means may prove useful and make the process more cost efficiant.

Conclusion:
This works
Also this means that substitution with MeOH will yeild formates With the addition of lead carbonate one could use that to prepare anhydrous formic acid from the lead formate or 75% from sodium formate.

Since not many people will be apt to use there H2O2 on GAA synthesis never fear because there is an alternative that yeilds better in the paper Iv attached. This uses an ozone generator to perform the same thing which I will like to test in the near future. This is great from my perspective because I get my GAA from sodium acetate so anything that could make the easyer makes me happy. Once an Ozone generator is contructed one will have large amounts of AcOH and formic acid at there hands cheep and easy.

Half cocked. .

The fentons reagent was no doubt producing acetates, very clean ones at that I might add(this aint no vineger made junk) , and a decent amount of them for the scales I was working at but it was killing my stash of H2O2 so I did not take it much further. I try to keep the H2O2 explictly for peracid synthesis since that was its reason for being purchased. Basicly the fentons reagent boiled down to a matter of economics in the end. While its all fine and well to produce these from easy to obtain things the price of a gallon of AcOH I fell could quite possibly top a couple hundred dollars.

Never made the O3 generator since Im side tracked way to easily. That kind of sucks to because I have alot of faith in it being a very cost effective means of getting cheep AcOH. I just started working on other electronic shit when I busted out with the high voltage gear and its kind of what lead up to the persulfate cell at the time.

Please, I need no inspiration at the moment to make one because due to my ADD I have to much going on and its a bitch to keep notes and everything in its place and you pile so much on you plate at one time like I have a habit of doing.... I will make the O3 and report back in due time I promise.

Hence the reason I have my random experiment threed... to remind me of which jerking off projects where worth another look.

O3 definitly worth another look but where as effective the fentons is not so much worth it.

I would worry about trying to oxidise larger substrates just due to the nature of the fentons reagent. Its so agressive I wouldn't doubt it to produce trace amounts of formic and shit from suger the way it just rips organics apart. O3 acts simularly but atlest that dont self catalyse itself into a hell storm of a reaction.

Just for shits and giggles get some Fe(II) salt(I use the sulfate) and drip some 35% H2O2 on a SMALL pile of it and feel the burst of heat that comes off when the drop hits and instantly vaporises. Its like a microscopic atom bomb went off. I would love to see a pint of H2O2 on a kilo of Fe(II). If you added organics to a mix like that you can bet there will be fire..... explosion.

Random time:
97.10 g/mol Sulfamic acid(H2NSO3H)
32.05 g/mol Methyl alcohol

1 to 1 ratio will be added to a flask with a slight excess iof MeOH and refluxed in hopes of forming ammonia methyl sulfate to observe the reaction in full. Wish me luck because this can be rearranged into Methylamine at high temperatures.

Peace
~Sedit

Edit:

Scratch that the Sulfamic is to bulky for a 1-1(maybe not but...) so .5 to 1 has been employed.

Edit2:

Does anyone think that H2O should be added for this reaction? Im kind of winging it here at the moment hence the reason its here under random
But it does not appear to be reacting after one how as the sulfamic is still completely there. When first added the MeOH took on a yellow hue but nothing more has seemed to happen. Im sure there is trace H2O in there but nothing significant perhaps if I could increase the solubility a bit more for the sulfamic I would get some sort of result.

Thank you V16. I have a very reliable source of 35% right down the street but its a little mom and pop type store so Im not to fond of buying it every couple weeks if you know what I mean. I just conserve now but would love to be able to experiment more the way I want to.

Ill look into it a bit more.


Edit:

Hmmm water it is... H2O apears to be needed for  the ammonia methyl sulfate synthesis else nothing much happends yet it appears to forms a thin layer of something yellow on the top after a while. Im assuming this is the ester im looking for but the condenser has fucked up because I was not paying attention and to busy arguing with baby mama drama and allowed to much heat IE alot of MeOH has been lost.

How did this sulfamic acid reaction go? Ever get any results?

Someone over at SM just had success with this. They used (Anhy)MeOH and dissolved all there sulfamic acid. As happy as I am he found success this bugs the hell out me because all I can figure is that my Sulfamic acid has gone bad over the yeilds because it hydrolyses with H2O.

So as it stands now no water should be used because it will destroy your Sulfamic and there are reports that it went fine. To me if all this pans out in the end this will be a great way to yeild one MeNH2 from easy to get chemicals.

Nope no hydrated form of sulfamic acid exist I dont think.

But the problem lies even deeper then that anyway as I dont believe my sulfamic is what I thought it was. After adding NaOH there was no smell of ammonia at all so I have no idea WTF this stuff is. We used sulfamic for septic systems all the time and this bottle looks exactly like what we used to use but I dont believe its sulfamic at all unless its totaly decomposed which could be possible given its age. Im gonna go try to get somemore within a day or so. Its cheep and so is MeOH so its not really killing my buget or nothing.

Awesome you've had success with this! Think it is one of the better ways to MeNH2, or have you not had time to get any pure MeNH2?