Sciencemadness Discussion Board

Hydrogenated of mesityl oxide with acetic acid

andy - 16-11-2013 at 22:35

Hi
Can mesityl oxide be hydrogenated with glacial acetic acid, or other acid and maybe some other chemicals?

I don't want to use hydrogen and Pd catalyst.

Thanks

Random - 17-11-2013 at 06:49

There is no way this could happen with only acid, maybe fe/hcl or something similar like zn/acoh. But these are very drastic reductions, often resulting in alkanes when starting from ketones. Which product do you want to obtain?

andy - 17-11-2013 at 09:28

Methyl isobutyl ketone , would isopropanol or Formic acid work?

plante1999 - 17-11-2013 at 09:54

You seriously need to learn chemistry, it is not because something can be oxidized that it will reduce chemical. Go learn a bit, tip:

Ammonium formate + Pd Cat
HgCl2 + Al

deltaH - 17-11-2013 at 11:51

plante1999, would the use of Al in this case not result in poor selectivity by way of reduction of the carbonyl? Also, did you not mean HgCl2 + Al + iPrOH? I have no experience with Al reduction like this, so just curious.

[Edited on 17-11-2013 by deltaH]

Random - 17-11-2013 at 12:02

Al isopropoxide may work but I am not sure, it is more mild stuff
Still would reduce ketone to alcohol iirc, not sure about double bond

HgCl2 and Al will probably reduce to alkane like metal acid reduction

You need to reduce double bond while leaving ketone group intact which would mean hydrogenation with hydrogen and pd/c probably

[Edited on 17-11-2013 by Random]

plante1999 - 17-11-2013 at 12:02

Poor selectivity, probably, although it would at least give some yield. I read about isopropoxide reduction, but I doubt it apply in this situation.

Random - 17-11-2013 at 12:06

Considering double bond reduction proved to be sucessful only with Pd/C in rheosmin and zingerone threads everything else would be not selective. If this may work then zingerone could be made from unsaturated ketone from isopropoxide.

deltaH - 17-11-2013 at 13:19

Hold on, I'm still confused here...
Quote:
HgCl2 and Al will probably reduce to alkane like metal acid reduction
Where does the hydrogen come from? The reason I added the iPrOH is because I assumed you still needed a hydrogen donor?

andy, why are you keen to avoid Pd/C, I think any other way is bound to be (a)harder, (b)more expensive, (c) lower yielding and (d) a bigger headache :P

Remember, you can recover your Pd/C by filtration.

Is your worry that you don't want to hassle with H2 gas supply? That might be solvable by using formic acid as a hydrogen source with Pd/C as mentioned. Also, you can construct a simple water electrolysis cell to supply you hydrogen that can bubbled directly to your hydrogenation setup. That way you can generate large amounts of hydrogen as a steady stream for long periods of time and it would be cheap... well minus an initial investment into decent electrodes.

[Edited on 17-11-2013 by deltaH]

andy - 17-11-2013 at 13:45

deltaH
It was just the cost of Pd, thought there might be a cheap way :), and would have gone down the electrolysis route, have got some carbon/Ti electrodes

Adding NaOH to acetone makes red diacetone, adding acetic acid and water turned it yellow, I'm guessing mesityl oxide , is this formula correct
CH3C(O)CH2C(OH)(CH3)2 + 3 CH3CO2H + -4 H2O = 4 CH3C(O)CH


[Edited on 17-11-2013 by andy]

deltaH - 17-11-2013 at 14:51

If you find that carbon anodes have insufficient durability for your water electrolysis needs, consider using IrO2/Ti anodes. It is my understanding that these are favoured for water electrolysis.

andy - 17-11-2013 at 22:33

Trying to get my head around the experiments, does this formula make sense?
CH3C(O)CH + H2O + NaOH = CH3OH + CH3COONa
Mesityl oxide + Water + Sodium hydroxide = Methanol + Sodium acetate

Thanks

Random - 18-11-2013 at 07:25

DeltaH hydrogen would come from the water as Al would be dissolving.

Andy, your last post makes no sense. No way this could be done.

andy - 18-11-2013 at 09:55

When I mix NaOH or ethanol with the mixture crystal form or a white gel, could it be sodium propionate and Ethyl propionate?

Random - 18-11-2013 at 10:29

No way... You barely know anything about organic chemistry. Please read up on some reaction mechanisms and function groups. Wikipedia will be a good read here.