Sciencemadness Discussion Board

pentaerythritol from methanol and ethanol

menchaca - 3-11-2003 at 12:16

hello! i´ve thinking that maybe possible get pentaeretrithol using a mixture of ethanol and methanol, oxidiying it in basic media maybe with KMnO4 and NaOh or something so.. of course this is just a idea and don´t know at all if this would work or not i really don´t see why this wouldn´t, but.. well some idea? Thanks!!

Edit: Title spelling.

[Edited on 4-3-2005 by chemoleo]

Onepot = no

PrimoPyro - 3-11-2003 at 12:23

I don't think it can be done in a one pot,and you will have problemswith oxidation using KMnO4, it has a tendency to oxidize alcohols to acids.

menchaca - 3-11-2003 at 12:30

well the oxidicer was just an minor important detail for me i was more interested if this was possible to make it directly from methanol and ethanol. what about other oxidicers MnO2, K2Cr2O7..

chemoleo - 3-11-2003 at 12:36

I think there was another thread on pentaerythritol
... KMnO4 indeed will oxidise ethanol to acetic acid, and you can obtain H2CO easily OTC, so no need to bother with this...
Now, acetaldehyde can be made with the K2Cr2O7 method, again I think it was mentioned in the Acetaldehyde thread.
Once you got those two reasonably clean, you can roll :)

Another reason why that two in one approach would likely not work (say, if you used the perfect oxidiser that would only form the aldehydes, but no acids) is that you would get side products, and quite a few of them. For instance, nascent acetaldehyde would potentially react with unreacted methanol to form acetals (hell, it would of course react with ethanol itself too). Many other reactions are possible, not just the pentaerythritol one.
To retrieve reasonably pure H2CO and CH3CHO from it would be quite a task.
Also, the aldehydes are generally formed under acidic condtions (i.e. with dichromate), while the pentaerythritol reaction takes place under basic conditions (in the presence of Ca(OH)2).
So better make those aldehydes separately I should think :)

menchaca - 3-11-2003 at 12:48

well is just a pity....:( it would have been so beautiful....snif,snif thanks all

vulture - 3-11-2003 at 12:56

KMnO4 acts as an oxidizer in basic media too. You'll just have to find the right redox sequence.

How bout MnO2? Much more selective.

Well, How about this?

PrimoPyro - 3-11-2003 at 13:05

The main reason I don't think your idea will work is because methanol, when oxidized to formaldehyde, will not stop. KMnO4 easily oxidizes formaldehyde to formic acid.

The reaction of acetaldehyde and formaldehyde to form pentaerythitol is called the Tollins reaction, and I detailed it very specifically at the E&W Forum over a year ago.

The reaction uses calcium hydroxide as a catalyst, and there is a careful equilibrium between the alcohols and some byproduct formic acid. By having so much more formic acid in solution from oxidation of formaldehyde, the equilibrium is changed.

Also, excess acids in solution will destroy the needed hydroxide ions to start the reaction.

A better route would be to use dehydrogenation instead of oxidation of the alcohols. Unfortunately this increases the cost and also lowers the over-the-counter-ness of the reaction.

But what about not making PETN exactly? Don't you think that the exact same compound, with one of the leg -CH2ONO2 groups changed to a -CH2NO2 (elimination of an oxygen, changing the nitrate to a nitro compound) should also be very powerful? I think so. This is much easier to make if you can't get acetaldehyde.

The same Tollins reaction, replacing acetaldehyde with nitromethane, will yield the compound I described above.

PrimoPyro

Mumbles - 3-11-2003 at 16:32

Just a theory, but what about mixing the components and vaporising. Then pass the vapors over hot Copper filings to reduce both to the respective aldehydes? I know that dehydrogenation only goes to the aldehyde stage. So the over oxidation would be prevented. They're both soluble in water so it may be a suitable solvent.

I really don't know if the diluted chemicals would work though. Maybe keep the temp in the recieving receptical cold enough to condense the acetaldehyde and bubble the resulting Formaldehyde into water. React then. It all would work in theory.

[Edit] Damn, I swear the stuff about dehydrogenation mentioned by PrimoPyro wasn't there 5 minutes ago.

[Edited on 11-4-2003 by Mumbles]

KABOOOM(pyrojustforfun) - 4-11-2003 at 20:03

<blockquote>quote:<hr>But what about not making PETN exactly? Don't you think that the exact same compound, with one of the leg -CH2ONO2 groups changed to a -CH2NO2 (elimination of an oxygen, changing the nitrate to a nitro compound) should also be very powerful? I think so. This is much easier to make if you can't get acetaldehyde. <hr></blockquote>
actuelly with one of the leg -CH2ONO<sub>2</sub> groups changed to a <b>"-NO<sub>2</sub>"</b> thus OB is perfect!:
O<sub>2</sub>N-C(-CH<sub>2</sub>ONO<sub>2</sub>;)<sub>3</sub> <s>&nbsp;&nbsp;&nbsp;></s> 4CO<sub>2</sub> + 3H<sub>2</sub>O + 2N<sub>2</sub>
it's a liquid exlosive with a VOD of 7860 m/s. megalomania's site has recepies for both NIBGTN and trimethylolnitromethane.

Rosco Bodine - 31-10-2006 at 11:09

Quote:
Originally posted by menchaca
hello! i´ve thinking that maybe possible get pentaeretrithol using a mixture of ethanol and methanol, oxidiying it in basic media maybe with KMnO4 and NaOh or something so.. of course this is just a idea and don´t know at all if this would work or not i really don´t see why this wouldn´t, but.. well some idea? Thanks!!

Edit: Title spelling.

[Edited on 4-3-2005 by chemoleo]


I stole your idea :D Sue me :P

Anyway , it is a good idea and there could be a way .
Recently there is interest in an electrolytically produced
manganic oxidizer , which might be worth experimentation ,
for a mixed alcohols oxidation to their respective aldehydes
needed for pentaerythritol .

It would be beautiful if it works .

If simultaneous oxidation of the mixed alcohols is
complicated by unwanted side reactions , then it
should still be possible to form the aldehydes separately ,
by dividing the bulk manganic reagent into proper
proportions , performing the oxidations and filtrations
in separate vessels , and then combining the liquids
for the production of the pentaerythritol .

[Edited on 31-10-2006 by Rosco Bodine]

chemoleo - 31-10-2006 at 20:00

One problem I can see right off..... alcohols react with aldehydes to form acetals. The yield will be undoubtedly lowered because of formation of acetals during the oxidation by manganous alum, because nascent CH2O/CH3CHO can react directly with alcohols that are still present.

Nonetheless I think it's an idea worth pursuing...maybe not in the context of a one pot synth of PE, but acetaldehyde or formaldehyde to start off with.

The problematics of this reaction depends a lot on the reaction rates of acetal formation. Since formaldehyde is easily available (at least here in the UK, when I bought it 6 years ago from farm supplies), why not just oxidising ethanol on its own? I'd love to see the efficiency of the reaciton. The alternative reaction with potassium dichromate works too but is not regenerable, requires destillation, and is prone to overoxidation to acetic acid. I wonder if manganous alum is simply a better oxidant. I shall be testing the making of this compound shortly, since I now have a lovely power supply.

Rosco Bodine - 31-10-2006 at 21:01

Another potential problem is polymerization of the aldehydes from the sulfuric acid formed by the oxidation . It would also be in the filtered liquid from the oxidation to complicate things . So on second thought ,
this would probably not work as a one pot reaction .
The oxidation would have to be run warm and with the
slurry thin enough to allow the acetaldeyde to boil out
freely as fast as it forms , and be distilled out of the reaction mixture , perhaps absorbed by bubbling the vapor directly into crushed ice and water , in a flask
sitting in a salted ice bath .

Acetaldehyde is really the important component to gain here , since paraformaldehyde or trioxane are easily available and easily converted to formalin .

So if all we can do is get an efficient method for acetaldehyde , then this manganic oxidation scheme
is a valuable tool for synthesis of the pentaerythritol .

The_Davster - 31-10-2006 at 22:52

But acetal formation is an equilibrium reaction, you have to activly remove water by dean starking or whatever method.

A while ago I tried a refluxing mix of EtOH, MeOH and CaOH, with a glowing Pt wire just below and to the side of the reflux collumn. I figured this method perhaps viable, but the damn thing kept catching on fire, as I took no precautions to exclude O2.

Cloner - 1-11-2006 at 08:49

The canizzaro reaction to PE is a bitch to work up. In the end you will have a lump which contains PE and may need further purification. If there's not much else in there to begin with, you can get an adequate quality of PE. But if you add side products of previous reactions it will be much worse.

[Edited on 1-11-2006 by Cloner]

Sauron - 23-12-2006 at 06:19

There's lots to do with pentaerythritol once one has it that aren't as antisocial as PETN.

Spiro compounds come to mind, spirolactones for example. Often very pretty molecules.

If one wants to eschew handling fots of formalin, there's paraformaldehyde and tere's trioxane, much more convenient. I don't recall the particulars of whether or not they can be employed to advantage in the prep of PE but then I haven't looked at this rxn in several decades

jon - 23-12-2006 at 11:59

PARAFORMALDEHYDE AND TRIOXANE will easilly hydrolyse in the prescence of a base there was a discussion about this some time ago but there is an optimal amount of base to use , as too little = no hydrolysis, and too much canizzaro reactions.
B.T.W. i remember seeing a PETN synth using hexamine and nitric acid does this work?

[Edited on 23-12-2006 by jon]

Sauron - 23-12-2006 at 17:14

I believe that's the usual path to RDX etc not to PETN. The former is a nitramine, the latter is not. Hexamine (urotropine, HMTA) does have a number of synthetic uses, generally as a formaldehyde source but getting to PE does not seem likely to be among them. It'd be going to Seattle to get from NYC to Buffalo.