Author Topic: Toluene Oxidation.  (Read 581 times)

Sedit

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Re: Toluene Oxidation.
« Reply #20 on: June 14, 2009, 04:50:02 PM »
Eugenol to Vanillin don't make much sence to me. Isoeugenol I could see being cleaved when oxidised but I don't tink eugenol will get there. Also to oxidise isoeugenol all the way to vanillin it normaly takes a stronger oxidiser and this seems gental compaired to harsh oxidisers like KMnO4 or O3 that normaly gets used. I feel this will convert Isosafrole to MDP2P and not oxidise it all the way to the aldahyde can anyone back me up on this?
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Re: Toluene Oxidation.
« Reply #21 on: June 14, 2009, 09:24:02 PM »
Wouldn't KMnO4 kick it all the way to the carboxylic acid? I know using KMnO4 it is difficult to get aldehydes from it.

Depending on time, temperature and quantity I think Mn persulfate can actually be a pretty strong oxidizer, I've heard people talk about benzoic acid forming from the toluene oxidation.

I bet if the temperature were mild and with maybe stoichiometry or less amounts of the oxidizer you could probably yeild what you'd like. Not sure though, and it might be a daunting task to figure it out.
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Re: Toluene Oxidation.
« Reply #22 on: June 14, 2009, 11:07:32 PM »
Check the patant that I attached a few post ago. They state that in order to get the carboxylic acid alot longer reaction time and a change in the ratio of water(IIRC) to favor the carboxylic acid over the aldahyde. Also Higher temperatures are used so where as some Benzoic acid may form it is by far the lower of the two products and some over at SM suggest a higher amount of toluene would remedy this.

I think your correct about KMnO4.

So if I decided to throw some safrole into the black solid oxidiser(the good shit) what will be the product? Isosafrole I have much confidence in but safrole not so much.
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Re: Toluene Oxidation.
« Reply #23 on: June 15, 2009, 07:14:47 PM »
I think methyldioxybenzaldehyde would form, but thats just because SM people say eugenol turns to vannilin.
try it if you can spare the stuff, and see what you end up with? Be very interesting to hear the results.
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Re: Toluene Oxidation.
« Reply #24 on: June 16, 2009, 08:56:08 PM »
to make the Mn persulfate, does the mixture while it is electrolyzing need to be heated?
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Re: Toluene Oxidation.
« Reply #25 on: June 16, 2009, 09:41:22 PM »
Nope.

 Just a divided cell with the MnSO4 / 60%H2SO4 as the anode mixture. It will go in that sand color and come out red/ purple/ or black depending on how long its run. Cool to watch honestly as the red pures off the anode. Good stirring will speed things up dramaticly and the higher the amps you can put into it the faster it will run. Your running a larger amount then I was from the looks of it so I would most definitly keep it stired or if you dont have an over head stirrer just give it a quick stir hear and there when you check on it.
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Re: Toluene Oxidation.
« Reply #26 on: June 16, 2009, 09:56:52 PM »
Yeah haha this has turned into a project bigger then I wanted it too actually.

I didn't think it had to be done with heating, but then I saw a few pictures and read a few things and I got confused.

Think it could be done safely in a plastic gallon bucket?

Of course it won't be all the way full of stuff, but its just what I have on hand since my 1 L beaker is about 1.3 liters to small lol.

If it can be done in a bucket, I'll get a nice set up going I think. I have been working on a jimmy rigged over head stirrer out of a blender as seen on the rhodium archives or whatever.

Figure i'll put the acid on the outside of the pot in the bucket, and the pot on the inside. I'll have a few rods holding everything.

If not a plastic bucket, not to sure what to use for this volume of material.
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Re: Toluene Oxidation.
« Reply #27 on: June 17, 2009, 03:50:30 AM »
Yeh a bucket will be no problem. You dont have to stir it to start getting results and if I was youI would just put some water in a bucket right now with the cathode, Place you flower put in the water with the anode and add the MnSO4 you have to the flower pot and plug it in. You will see the pink start comming right away as soon as you add A little bit of H2SO4 to the cathode compartment. ....  Itll keep your spirits up ;).

This is one of those projects that COULD be taken to the extreams and a great setup could be made... But if your looking to get your feet wet with a new form of chemistry this don't take much at all. Just try not to over think it brother its just electrolysis with a divider that works on a simple level and has many areas that can be tweeked for improvments.

Plus once you get the use of the cell going nicely you have a whole mess of new reagents at your finger tips like many persulfates and permangenates, perchlorates. And something I REALLY want to try is isopropyl hypochlorite. This has the ability to quickly turn toluene into BnCl without the hassles of Cl2 free radical oxidation. I would have to modify a bit though to make sure the cell is damn cold because its not the nicest of reagents as far as I understand.
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Re: Toluene Oxidation.
« Reply #28 on: June 17, 2009, 05:02:06 AM »
yeah, explosion hazard?

I just want to make sure I do this correct. I'll make a 55% soln. of H2SO4 and add my MnSO4 to that and start electrolysis of it tomorrow I think. I'll have about 2.5 liters I believe.

This project is actually really helping my chemistry out. I've finally completed my overhead stirrer for it, and I'll be able to get lots of things as you mentioned.


What do you think it will do with styrene? That might make a nice product there. I'd guess phenylacetaldehyde?
That is at least what it would do with phenylethane I'd think.

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Re: Toluene Oxidation.
« Reply #29 on: August 04, 2009, 03:32:25 AM »
Well just finished up a nice run of BnO waiting for it to finish now and the smell got me thinking about MePhBuO again. So why searching thru the hive for any gem I could on Methyl Phenyl Butenone I came across this.
Now normaly Im not a big fan of copy paste from old forums but I think this brings up many good points such as storage stability of the oxidiser and the transference to something other then H2SO4 for use in other applications. Also it denotes how to make it non electrochemicaly.




Quote
hermanroempp
(Hive Bee)
09-14-03 16:12
No 459026
         Just another oxidiser - Manganese-(III)-sulfate
(Rated as: excellent)       

Process for the preparation of an oxidiser:

The process implies the dissolution of manganese-IV-dioxide in sulfuric acid of 50-60% strength in the presence of manganese-II-sulfate. To obtain the oxidiser as a solid, a cold saturated solution of manganese-II-sulfate in water is prepared and concentrated sulfuric acid is added (with cooling, of course) until the solution contains 50-60% sulfuric acid.
The purpose of precipitating the manganese-(II)-sulfate by addition of sulfuric acid is to get the sulfate in finely divided particles, but finely ground manganese-(II)-sulfate could also be used with the same results.
To the crystalline sludge such obtained an equimolar part of manganese dioxide is added under strirring, i.e. for 1 Mol MnSO4 1Mol MnO2 is added. The slush is stirred until the manganese dioxide has dissolved under warming (the reaction is exothermic).
On cooling or upon addition of more (cold) concentrated sulfuric acid the oxidiser settles out in the form of lustrous, brown-red needles.

The product such obtained can be dissolved in organic acids, like acetic acid, and can be used in such solution to react with dissolved organic compounds which otherwise would be destroyed by concentrated sulfuric acid.
The oxidiser itself remains unchanged in its solid form if all traces of water are excluded.


[Translated from:  D.R.P. 205200, titled "Verfahren zur Herstellung eines Oxidationsmittels"]

Italics mine

The reaction involved in this process is:
MnO2 +MnSO4 +2H2SO4 --> Mn2(SO4)3 +2H2O

The preparation of this compound is comparable to the prep. of Mn-(IV)-sulfate, as described by neograviton, but the need of working with fuming hot sulfuric acid is omitted, which seems to be a little healthier...
Also, like in neograviton's preparation, there is no need for purchasing watched items like potassium permanganate for the preparation of activated manganese dioxide

An educated guess at last:
For the preparation of benzaldehyde from toluene, I think the procedure described by neograviton should work equally well with the use of abovementioned Mn-(III)-sulfate, there is even no need of isolating this compound from the 60% sulfuric acid solution, use it as it is.
 


BTW I accidently left my cell on for almost 48 hours this time with only 64 grams of MnSO4 in a small cell at about 20 amps.

Well acid mist means I lost alot of my solution to the air because it wasn't covered but I was left with a VERY black material this time. Normaly there is almost a hint of gold color but not now. Now it is pitch black. Annnnndddd At Roughly RT is smelling the place up like BnO just with a little magnetic stirring.
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Re: Toluene Oxidation.
« Reply #30 on: August 07, 2009, 12:22:11 AM »
After regenerating my oxidiser I have some questions that I hope ya'll maybe able to answer.

When forming persulfates like Sodium persulfate and ammonia persulfate via electrochemical synthesis heat is your #1 enemy and unless the Sodium persulfate cell is kept at a low temperature the persulfate is destroyed. Mangnese persulfate is no exception in that when heat is applyed you can see the persulfate being destroyed by changing from black to a sand like color. The "problem" arises when testing the running temperature of my cell and it runs at 124 degrees F. This is more then likely destroying some persulfate as its being formed and I wounder if an even higher oxidation state could be achived thru the use of lower temperatures. Possibly even reaching the VII oxidation state what ever structure that may be.

Another issue that I am having with the cell is even with it mostly covered I am losing alot of H2O because of the heat and what is suppose to be a known concentration of H2SO4 is no longer that after the oxidiser is regenerated.

Also while searching I found out that KMnO4 treated with H2SO4 yeilds Mn2O7 which can further react to give the MnO3+ cation which has simular properties as Chromium trioxide which with the addition of HCl forms Chromyl chloride. Chromyl chloride is well known for its ability to oxidise toluene in high yeilds to benzaldahyde but its use is discouraged because of the strong cancer causing properties of hexavalent chromium (CrVI). Does anyone think it may be possible to synthesis a simular reagent using MnO3+ and acheive simular results given there mode of action? Perhaps a safer alternative to Chromyl chloride?

I will keep looking into this but anyhelp from the more informed wasp here would be greatly appreciated .

::[Merged post]::

I have found the formulas thru which Mangenese Trioxide forms.

2 KMnO4 + 2 H2SO4 ? Mn2O7 + H2O + 2 KHSO4


Mn2O7 + 2 H2SO4 ? 2 MnO3+,HSO4- + H2O

Issue seems to arise given the fact that Mn2O7 is a volitile extreamly strong oxidiser that sublimes at -10C and at 55C it decomposes explosively. I still have yet to find any information of how MnO3+ would react with HCl.

Given there simular properties I can't help but wounder if K2MnO4 + HCl followed with H2SO4 as a dehydrating agent as per the prep for Chromylchloride which uses K2CrO4 + HCl + H2SO4 would yeild the equivalent Mn based compound.

And if so will the substance be as cancer causing as chromyl chloride?

I use to be able to figure this kind of shit out just looking at the reaction but as time goes on Im quickly lowering from scientist to mad scientist to just plan mad.

::[Merged post]::

Yeh Yeh Tripple post yada yada but Im experimenting here gimme a brake.

This is very interesting to me because it proves everything I just talked about.

After shutting down the completely regenerated cell and allowing it to cool to about 84 degrees F I start it back up, the Smell of OZONE is strong. This may not mean much to you but to me it means exactly what I have been thinking.

The cell has been running completed for sometime yet I could not smell ozone. Due to the heat it can not reach that oxidation state of Mn2O7,  However when allowed to cool it can.

But..... Mn2O7 decomposes to MnO2 + O2 + O3. The smell of Ozone must be comming from the decomposition of formed Mn2O7 and would explain why my cell has gotten so black when I never seen it do so under milder conditions.

I think what I need is some more H2SO4 in the mix to promote the MnO3 cation. I have a good feeling that this is the reason that this oxidiser can do what it does promoting the oxidation to the aldahyde and no further which most can not do.

Its just a hunch at the moment and Im going to ask some people over at SciMad who can clearify whats going on for me but I think with iced Diethylene glycol like I did with my Na persulfate then I could make a very, very potant oxidiser.

Must be testosteron but I have always been obsessed with more power from my chemicals.

 
« Last Edit: August 07, 2009, 06:08:01 PM by Sedit »
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Re: Toluene Oxidation.
« Reply #31 on: August 07, 2009, 06:49:08 AM »
Interesting, but be very careful Mn2O7 reacts explosively with organics and is a very strong and unstable oxidizer. http://www.youtube.com/watch?v=7j6RDeGgJPg

Not to sure how they MnO3 would react, but I bet it to would be to powerful of an oxidizer and bring it to carboxylic or completely destroy the molecule.

Edit: Think nitric acid can oxidize Mn sulfate to persulfate? That would be nice!
« Last Edit: August 07, 2009, 07:07:30 AM by Vesp »
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Re: Toluene Oxidation.
« Reply #32 on: August 12, 2009, 07:43:34 PM »
What do you all think of purifying my BnO thru freezing? -15F should be reachable with little effort(Although its to hot to try right now). I got about 300ml of unknown purity here and no Bisulfite. I was going to try to fraction it to the best of my abilitys but thats going to be difficult. CaCl2 and Ice should get me to -15 with a little room to spare and I know for a fact that Snow and HCl will quickly drop the temperature to -38F in a few seconds. Sadly this don't work the same with block ice and I don't think its going to be snowing anytime soon round here.
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Re: Toluene Oxidation.
« Reply #33 on: August 12, 2009, 09:10:57 PM »
I would try it at least, seems like it would be do-able. The freezing point of BnO would probably be different when it is dissolved in toluene, though I could be wrong.
There would still be difficulty totally separating it from the toluene as well, since the BnO would melt easily and could be coated in, and have toluene trapped in its crystals.

Isn't there something else that can form an adduct with BnO that could separate it, or it having a higher solubility, or insolubility in something that dissolves in toluene?
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Re: Toluene Oxidation.
« Reply #34 on: August 12, 2009, 10:07:31 PM »
Dunno I know ammonia forms an addition product with it that hydrolysis in H2O but I would think that the product would be BnOH instead.

Either way.....  I FOUND IT. Son of a bitches moved it on me and I have been looking for the last 3 months. But I have it....

So excited to get to test it I added about 5ml BnO to a test tube. Dissolved alot in another one till no more bisulfite would dissolve and added this to the BnO.....

WOOOHOOOO. The organic layer all but a few little drops went away. That means its almost pure BnO. It has a harser tone then I expected from BnO hence the reason I questioned purity but non the lest the Bisulfite don't Lie its about 300ml of pretty damn pure BnO. Im going to work the rest up later so that I can store the BnO like I want to instead of having to hurry and use it because of oxidation..

I was so happy when I found the bisulfite and now that I see this Im excited.
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Re: Toluene Oxidation.
« Reply #35 on: August 13, 2009, 05:08:27 PM »
Interesting that the larger batch I tryed produced little BnO :(. I thought that it would be the other way around but I think my oxidiser may have been contaminated or something. I have to go now to pick up some more EtOH for the adduct so I can be 100% sure but it sucks because that will mean I only have about 50ml at best instead of 300ml I thought.

I wounder because the patent stated 50-60 degrees C for the reaction to take place yet neograviton albeit created the Mn(IV) differently said to reflux the reactants for a few hours. Im slowly finding he may be correct where as the patent may BS a little bit. Time will tell and I have to recrystalize my Mn(II)sulfate a few times to purify it before I can move forward. Next time im going to just reflux and see what it yeilds.

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Re: Toluene Oxidation.
« Reply #36 on: August 13, 2009, 06:49:08 PM »
How is it you plan to separate the Mn Sulfate from the sulfuric acid?

You say it produced little BnO, do you know if it proceed a lot of benzoic acid, or just didn't react with the toluene? The concentration of sulfuric acid, as well as temperature plays a significant roll in what it produces.
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Re: Toluene Oxidation.
« Reply #37 on: August 13, 2009, 07:29:40 PM »
When you evaporate the H2O the MnSO4 drops to the bottom with ease. I was just going to filter and redissolve in some H2O to get the last H2SO4 out and recrystalize it. I will surely lose some MnSO4 in the process but atlest its pure.

I may be mistaken about the little bit of BnO being formed and ill have to get back to you later on that one.
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Re: Toluene Oxidation.
« Reply #38 on: August 13, 2009, 07:33:38 PM »
I see, so you must not be boiling it, since that'd produce Mn Persulfate, which would probably stay dissolved in the acid. So I guess just a low heat right?
 If you do boil, be careful not to get the vapors/Mn particles in a place where one might breath them.
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Re: Toluene Oxidation.
« Reply #39 on: August 13, 2009, 09:56:37 PM »
No I boil it. The persulfate don't form until you heat really concentrated H2SO4 at a high temperature for sometime. I think its formation is mainly due to SO2 and SO3 formation from the decomposing acid.

When I boil it down I feed the vapors into H2O anyway to prevent the H2SO4 from getting in the air. Im not to worryed so much about Mn vapors honestly. Thats a cathinone freak disease that comes from extream over exposure to it.
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