Author Topic: Toluene Oxidation. (Read 581 times)

Douchermann · « **on:** June 07, 2009, 07:18:49 AM »

Holy improved method batman. As much as I love cleaning glassware after a BnCl reaction... I might have to switch to this, since 95% of my BnCl goes into BnO. As far as water preventing your BnCl reaction... really? I've never had that issue before. I add water (water + HCl) if I'm using fresh toluene. In fact, there is usually a decent amount of water in there when I recycle my toluene (when I go on BnCl binges). Hmmm perhaps I will try this sometime. The only thing I don't like is that it requires a precursor somewhat unavailable in large amounts OTC (batteries would get expensive if you run a 5L batch).

Vesp · « **Reply #1 on:** June 07, 2009, 07:23:16 AM »

I can't find the very post on SM, but what about the Sodium persulfate (walmart) copper acetate, and Iron sulfate mixture used to oxidize toluene into benzaldehyde with what seemed to be around 90%+ yield.
I'll try to get some of that soon and try it out as I have everything else. If I can find the money for it, Isn't the sodium persulfate 15 bucks for only 50% or so? (but 5lbs)

Sedit · « **Reply #2 on:** June 07, 2009, 04:05:29 PM »

Klute just told me he has mixed feelings about the persulfate oxidation and that it can lead to runaways.

I just recently took my spent Mn Sulfate that was white and dumped it into the anode compartment of a divided cell. Passed some juice into it and the lead anode started to pour pink off the anode. The whole mixture after a fewe hours turned a deap purple and this was dumped onto toluene and stired with a slight heat. After about 1 hour(longer for larger batches) The whole mixture turned back to white/yellow the toluene was extracted and the smell of cherrys filled the air. Works great now its time to get my shit together and do it right.

If yall don't have one of these Mn persulfate cells get one. I made formaldahyde/acetaldahyde and benzaldahyde yesterday. Its visual clues to when its done are bar non and I would still have it running if I didnt blow out my power pack. No need to fuck with the harsh BnCl if you can go streight to BnO from toluene.

I really wounder how this would react with isosafrole. Its such a gental and quick oxidizer this could be a very quick and clean way to MDP2P.

Vesp · « **Reply #3 on:** June 07, 2009, 09:38:28 PM »

Thought I'd post this anyways! Glad to hear you have it going pretty well sedit, what does it take to make a cell like that?

Quote

Posted by Osmium at the-hive:
Quote:

Quote
Benzaldehyde

Ferrous-Copper Catalyst: Toluene (7.6 g.), water (35 ml.), ferrous sulphate
(0.110 g.) heptahydrate, cupric acetate (0.072 g.) and methanol (8 ml.) are
placed in a 250 ml. reactor.

Sodium persulphate (47.05 g.) in an aqueous-methanol solution of sodium
persulphate is added slowly to the mixture which is maintained at 70.degree.
C., in an atmosphere of nitrogen and under agitation.

The organic phase is separated after two hours and the aqueous phase is
extracted with ethyl ether.

The combined organic phases are distilled to afford 8.29 g. (95% yield) of
very pure benzaldehyde (compared against a pure sample).

US-Pat 4,146,582

/ORG

PS: Ammonium-persulfate should work too. Pleasse notive the big amount of persulfate needed. Smell of bitter almonds doesnt say much - it smells already in strong in traces in special when warm and with water.

[Edited on 27-1-2005 by Organikum]

Sedit · « **Reply #4 on:** June 07, 2009, 11:45:10 PM »

Its simple as baking a cake. And since I burn all my cakes(J/k) I would say easyer. Understand That I may have some of the principles a little off but its working regardless. Im also pretty sure that I have the neograviton principles a little off. He started it generates Mn(V) which I always assumed was a typo but since the color does not match the Purple Mn(IV)sulfate Im a little confused.

Either way here goes the basics.

Materials.
==========
Two flat lead electrodes
An unglazed flower pot with the hole epoxyed closed.
MnSO4
60% H2SO4
A DC wall adaptor. The stronger the better but something should be put in the circuit so that the adaptor don't over heat. (ill explain this some other time a better way to do all this no time to do it right at the moment)

Take some light pink MnSO4 and add it to a Eq Molar amount of 60% or so H2SO4 . You basicly want enough H2SO4 to create Mn(SO4)2 with some extra H2O. This is your anode solution. The cathode solution is just dilute H2SO4 enough to conduct electricity.

Epoxy over the hole in the bottom so its sealed.

Your cell needs to have a divider. This has been done over at SciMad with Tyvek suit which maybe better then my method of using an unglazed planting pot. The tyvek suit material is made to have a net positive charge for what ever reason and this can act simular to a salt bridge where the charge is swaped thru ions instead of the anode materials and cathode materials mixing.
I accomplish this by running epsom salt in both sides of the cell and putting the positive in the pot and let it run for a while to charge the pot. It dont have to be done but it increases performance.

Put the pot into a plastic or glass container and fill it with the MnSO4 solution. Put the dilute H2SO4 in the outer container.

Insert the lead electrods into there place one in the pot and one outside of it.

Connect the anode to the inside of the pot and connect the cathode to the outer solution. You can tell which is which because when both dipped in the H2SO4 solution the one that bubbles an ass load of H2 should go on the outside and the other inside the pot.

The Pinkish white MnSO4 solution will start to turn red at the anode. Its best to stir this solution(Something Ill get into when I explain how to stop the powersupply from overheating). As the pink pours off the anode the solution will progress to a deep purple. I have heard that with enough time it will turn black and this is when its some kind of super oxidiser and will give like 98% yeilds. Also more on that later.

These cells are great for making oxidisers and alot of other semi hard to synthesis chemicals by other means. Persulfates/perchlorates all kinds of shit. The pictures over at SciMad in the toluene-BnO threed show MAA oxidiser. This is basicly the same thing just with a divided cell to protect the charge instead of making the double Ammonia Mn salt in an undivided cell.

Thats the basics Sorry if this is a little confusing right now im in a rush so ill tell more later. Questions I can answer the best I can though.

Peace.

PS: go make one now an Ecell is the best thing to have around for all kinds of things.

V16 I know your pretty good at the Math of these things I believe right. Care to fill us all in here sometime.

Vesp · « **Reply #5 on:** June 08, 2009, 12:34:11 AM »

Interesting, I am doing a test run on making some MnSO4 from batteries to do some experiments with. I have a really nice power supply, and this is just the sort of thing I have been looking for.
Tyvek can be used? That is interesting, I have a bunch of tyvek envelopes that need a use!

I obviously need to read a lot more, but my time on the internet has been limited lately, but it sounds like the ammonium salt doesn't need to be divided? That might be useful, especially since ammonium sulfate is easy to get as a fertilizer, and what not.

Sedit · « **Reply #6 on:** June 08, 2009, 12:45:34 AM »

Funny thing about the batteries Vesp is people say you can't make MnSO4 Directly from the batteries and they say to make MnCl2 first by adding HCl and wait for the nasty ass Chlorine to stop comming off. I have found this to be not needed. Take all your battery guts and grind them very fine. Add H2O and boil to remove any ammonia chloride. Allow it to settle and decant because filtering is a bitch. Dont worry about the last bits of water. You can add a little bit of HCl now to make sure any Zn or Fe ions are gone but I dont think its really needed in most cases. Now just add some H2SO4 and boil the shit out of it till it is really concentrated and white fumes come off. At this point because of all the carbon everthing will be dry and hard as a rock. Get it out and grind it up again. Add some water and boil again. This time decant and save. Filter the remainder. Evaporate this water and you will have a pink or orange powder. Thats your MnSO4. Grind it and add a little H2SO4 and it will turn a pure light pink(like beach sand color) overnight. Atlest you dont waste a shitload of HCl and you dont have to worry about the Cl2.

Batterys suck and im looking for concrete black with is MnO2 but you have to make sure its not an Iron compound. I know they have it but I cant find it at homedepot or lowes so if anyone can give me a brand name that would be great. Its about 70% MnO2 from what I hear.

Vesp · « **Reply #7 on:** June 08, 2009, 04:33:37 AM »

I did a little test tube worth, took the MnO2 straight from the battery and heated it with strong H2SO4 (probably excess?). It seemed to dissolve when heated and turn into a black gunk when cooled. I heated it so white smoke came off, but it seemed like it wasn't nearly hot enough for that, so perhaps it was ammonium chloride, or HCl. I don't know, and I don't really care - but a gas did come off.
I added water and noticed a brown substance dissolve into the water. I shook it up a bit more and allowed the carbon to start to fall out and I noticed the solution was a pinkish color. I am coming back to it tomorrow to hopefully see a solution of MnSO4, and some black carbon on the bottom which will be separated.

And if that works well, I will do it on a much larger scale - I need to use up some more of my sulfuric acid, and 3-4 large D batteries have a decent amount of MnO2 in them so it seems.

Also, if you get the time I would like to see the structure of your partitioned cell. I have decided to start working on one and so far I only have a rubber cork in the bottom of a small tarracota pot.
Not to sure where to go from there , but I assume just put it mostly in the solution and start electrolyzing it. I'm worried the rubber stopper might fuck things up though.

Sedit · « **Reply #8 on:** June 08, 2009, 04:55:09 PM »

I have attached the patant for this and here is a link to the threed over at SciMad

http://www.sciencemadness.org/talk/viewthread.php?tid=6882&page=2#pid86424

Im going to take some pictures today and when I get it all organized im going to split this off into its own threed.

I do have good news. I let the cell run overnight and indeed the whole solution turned black which is the super oxidiser so to speak. I got some cruddy toluene left so Im just going to try and clean up about 50ml and toss it in to see what I can get.

I thought that if toluene was left in as the cell is running then benzoic acid would be mass produced like it does with the MAA oxidiser but I noticed that when it was put in as the cell was running the smell of BnO became very very strong within minuted so maybe a constant production could be considered with the toluene dripping in as the cells running and taken off the top to be seperated but I have no use for this much BnO at the moment.

Heres a threed on MnSO4 production.

http://www.sciencemadness.org/talk/viewthread.php?tid=6777

They appearently don't like my way of doing it but it works well for me;D.
Maybe Im getting junk yeilds or something but im getting alot more then I was ever able to isolate using a ton of HCl. Funny part is some in that threed are saying that the MnO2 can't react with H2SO4 but you will see for your self thats bullshit when you filter and evaporate that solution of yours.

Vesp · « **Reply #9 on:** June 08, 2009, 07:10:53 PM »

Thanks great sources. I don't know whats with that sciencemadness thread. MnO2 dissolves in hot sulfuric acid with out much of a problem. I assume that the pinkish solution is MnSO4. What else could it be? The SciMad people are smart though, so perhaps it works for us because our sulfuric acid, and especially our MnO2 if we are using it from batteries is impure and has oxidizable material in it. This could reduce the MnO2, and allow it to react with the H2SO4. Using pure H2SO4, and pure MnO2 might be a different story. Also if there were different metal ions (zinc, iron, ammonium, etc) it may also allow for it to be dissolved involving some mechanism. I have no idea.

After looking at the electrolysis method, it almost seems like heating it with more sulfuric acid is probably the way I am going to go about it, but we'll see.
Electrolysis seems fun, and I've never really had a chance to do it till now, now that I have the equipment.

'

Sedit · « **Reply #10 on:** June 08, 2009, 07:23:49 PM »

I have a feeling that as the H2SO4 is getting really hot and really concentrated it starts to break down to SO2+ H2O+SO3 ect... hence the white vapors.

The SO2 can react with MnO2 to generate MnSO4 so that may explain why the neograviton methode is told to be run that way. At first it forms Black crystals on cooling in a dark brown solution when done with clean MnSO4 + H2SO4 but with the addition of H2O and slight heat it turns to a peach color solid in a pink solution. The left overs from the neograviton method is how I found to just heat the hell out of it and extract your MnSO4. Its also what I used in the cell Im running now. Since Im only running small scale and not quite sure how much MnSO4 I added to start with I just added 30ml of toluene to the black mixture and set it on the magnetic stirrer to see if it will slowly convert at ambiant temperatures. I got pictures so when it turns back to MnSO4 i'll upload the pictures and report how long it took without heating.

[edit Fixed pictures also.]
Heres some pics of the cell. I used a wall adaptor and put a motor in series to prevent over heating of the adaptor. It normaly is used as an overhead stirrer but I lost my top and the stir bar broke off yesterday so i couldnt stir the mixture.

Vesp · « **Reply #11 on:** June 08, 2009, 07:35:46 PM »

bizarre the pictures are that big when attached in that fashion.. eh who cares.

That is interesting though, and looks very simple! using a smashed lead item on the outside for an electrode, right?

Thanks for the pictures.

Sedit · « **Reply #12 on:** June 08, 2009, 08:00:54 PM »

Yeh its old plumbing pipes beat down into shape and cut. My cell looks alot better then that but its in pieces at the moment and the stainless steel bowl I used for the outer electrode before decided to give out when I started this run so I replaced it real quick with a mini crock pot. I guess that could be helpful though for somethings to help keep them heated and in solution but I don't need that now just a matter of what was on hand. I have a plexiglass top with a hole in it for the stirrer but I can't find the damn thing.

Make sure that the adaptor you use is a spare because theres is a good chance that it may burn up so check it every now and then to make sure its not heating to much.
Also for a larger cell the adaptors will take forever unless you have 1000ma or greater. Im going to get a cheep battery charger from harbor freight sometime soon to use on these.

Keep in mind this is Pb and be careful with the shit. I was smoking a cig and could taste a little lead because of my hands I think. Just don't set the cell up anyware where you will be eating or working around alot. Stick it somewhere out of the way where you won't have to worry about Pb contamination carrying over on you later down the line.

PS: Im going to resize the pictures and put them inline when I finish everything Im doing. I didnt look at them but if they are the size the normaly are then they must be huge.

Vesp · « **Reply #13 on:** June 08, 2009, 09:41:22 PM »

yeah, the pictures make it annoying but I thought I set it so the uploaded pictures were all the same size? I'll look around and see if i can fix that problem but it seems like the quick fix is just to have you edit them.

Well, heating Battery MnO2 with hot sulfuric acid perhaps doesn't work that great. Though my separated solution turned brown, with black material on the bottom, with the addition of HCl a decent amount of chlorine gas was let off. I didn't see any bubbles but I could smell it. I'm just saying it doesn't get it all.

I recently heated the rest of my MnO2 with more sulfuric acid, and a little bit of sulfur to help dissolve most of it. I thought it would work better, and it probably did. I think/hope the reaction went something like this:

MnO2 + SO2 = MnSO4
S + H2SO4 = H2O + 2 SO2

I watched the sulfur melt and after I could smell SO2 even stronger then before, so I think it was a good choice. No sulfur is floating on top of my solution either so it must be gone (I think it is less dense anyways, if its at the bottom still isn't a problem though)

After heating it with sulfuric acid and sulfur I added water, let it cool and then noticed a bunch of black particles falling out - shiny and graphite looking, same as last time, which apparently had MnO2 in it since a Cl2 was released with the addition of HCl.
So I added HCl to this and of course, Cl2 was let off. I added a bunch and now it is sitting letting off some gases.

I figure:
MnO2 + 4 HCl ==> Cl2 + MnCl2 + 2 H2O
MnCl2 + H2SO4 = MnSO4 + 2 HCl

So some of the chloride gets recycled and is used to make more MnSO4, I'm just afraid that it might cause some weird equilibrium bullshit making the chlorine reaction go much slower. Either way since there is more H2SO4 in there then I should have put, HCl will be let off when I heat it up again after decanting off the solution leaving any of the graphite/carbon junk behind.

Vesp · « **Reply #14 on:** June 08, 2009, 09:50:10 PM »

Sorry I've been mostly talking about dissolving MnO2, but I figure it is important to know about.
After stirring my mixture again w/HCl added in a windy garage it is more then obvious I didn't heat it hot enough, or something (white fumes were forming) because a very considerable amount of Cl2 is being let off.

Sedit · « **Reply #15 on:** June 08, 2009, 11:35:27 PM »

To do away with using so much HCl try salt+H2SO4+Battery guts. This was not so ad when I did it on a small scale sometime back. You still have Cl2 to contend with but alest you are not adding a ton of H2O also to it. After this is done reacting Dilute and filter it. After that add saturated Sodium Bicarb solution and the Mn carbonate will fall out nicely. This can be reacted direct with the H2SO4. That is pretty much the standard for cleaning the batterys but your creating the HCl insitu instead and its way more concentrated.

Sedit · « **Reply #16 on:** June 09, 2009, 03:57:34 AM »

I let 30ml of toluene run in the black oxidiser with nothing but magnetic stirring and no heat for 7 hours and noticed no sign of color change.

So I set up a hot water bath that was not quite boiling to go along with the stirring and after about 2 hours you can clearly see the difference.

The top picture was before the toluene was added and in the bottom picture you can see the discolored toluene on the top. There is a big problem though as I said before the toluene was crap it was just a simple distillation of some wood stripper. There was a slight discoloration prior to addition but I didn't think that should hurt to much and it was all I had so since I was just playing anyway I used it.

Mistake. Whatever wood oils that where in it polymerized or some shit because that whole top layer you see there turned into a goop of sorts on cooling. There may be some BnO there but it is being over powered by something else. Ill distill it tommorow and let you know what I find out. FYI Im having more issues with this so far in the first couple of runs way more then I did with the neograviton method. EtOH and MeOH oxidation seem to happen with ease so BnOH more then likely would to but im getting a harse note on top of the toluene oxidation.

Vesp · « **Reply #17 on:** June 09, 2009, 07:16:35 AM »

Interesting, at least it is obvious that the Mn salts are oxidizing things. This means it probably works, but you just need to get better toluene.

Sedit · « **Reply #18 on:** June 14, 2009, 03:20:03 AM »

Its killing me and I get find the answer anyware.

What will this do to safrole, isosafrole, or styrene? The double bond confuses me so I wounder if any of you know what would be the product.

Vesp · « **Reply #19 on:** June 14, 2009, 08:42:53 AM »

Cycloknight from SM claims that eugenol can be oxidized to vanillin. No one seems to have tried this and I don't have any other references, but my guess is you'd get the benzaldehyde derivatives.
However, temperature and a few other things can be altered and I bet you could make other things instead of the aldehydes.
I'm sure it could oxidize secondary alcohols to ketones.

Author Topic: Toluene Oxidation. (Read 581 times)

Douchermann

Toluene Oxidation.

Vesp

Toluene Oxidation.

Sedit

Toluene Oxidation.

Vesp

Toluene Oxidation.

Sedit

Toluene Oxidation.

Vesp

Toluene Oxidation.

Sedit

Toluene Oxidation.

Vesp

Toluene Oxidation.

Sedit

Toluene Oxidation.

Vesp

Toluene Oxidation.

Sedit

Toluene Oxidation.

Vesp

Toluene Oxidation.

Sedit

Toluene Oxidation.

Vesp

Re: Toluene Oxidation.

Vesp

Re: Toluene Oxidation.

Sedit

Re: Toluene Oxidation.

Sedit

Re: Toluene Oxidation.

Vesp

Re: Toluene Oxidation.

Sedit

Re: Toluene Oxidation.

Vesp

Re: Toluene Oxidation.