Sciencemadness Discussion Board - OTC tert-Butanol

OTC tert-Butanol

ScienceHideout - 29-8-2012 at 17:28

Hi! I just saw a post on here that said that a member got t-BuOH from the octane booster "turbo octane booster 108."

Once I read this- I hopped in the car and drove to the autoparts immediately and bought a bottle. :-)

The member says that they took it and mixed it with water and shoved it in the freezer. They say they then decanted the non-frozen stuff and kept the tert-Butanol crystals.

I have a bit of t-BuOH... I know it forms jellyish crystals just below room temp... In fact, my vial is usually about half-jelly.

I did a couple extra steps... I poured the fluid into a sep funnel and shook it with a bit of H2O (1/2 the volume of the booster).
I then drew off the bottom layer... It smelled sort of rubbery- similar to pure t-BuOH. However it was not flammable (I tested).
5 minutes in centrifuge to ensure it separated.
Into the freezer- 30 minutes- I saw no BuOH crystals... ?

What did I do wrong? Should there have been additional steps to purify it? Is there an alternative way?

I've seen it elsewhere online that says this brand I used contains tert-Butanol...

Rogeryermaw - 29-8-2012 at 19:14

http://bluemagicusa.com/bm_files/msds/Turbo%20108%20Octane%2...

says kerosene, Methylcyclopentadieyl manganese tricarbonyl, and 1-5 percent of an undisclosed mixture which, even if it was tert butyl alcohol, wouldn't be worth the trouble for that amount at the price per bottle.

Wizzard - 29-8-2012 at 19:36

That was me

And I am uncertain of my success... What I had seemed to have the right properties, but I ruined the whole batch trying to dry it with a salt.

My process was trying to use the properties of the t-butyl alcohol and water at temperatures- I know it's water soluble more than other things, so an amount of it would be stuck in the water as it froze, but most of the other parts of the gasoline additive were not able to be frozen, so it could be decanted. Then I tried to separate the t-butyl alcohol from the water... I had some being distilled, but it did not come out well

I had put the project on hold until I was able to source some actual t-butyl to compare with my results from the Turbo 108.

[Edited on 8-30-2012 by Wizzard]

Wizzard - 29-8-2012 at 19:47

Also, the govt's MSDS for Turbo 108 lists different CAS numbers:
http://hpd.nlm.nih.gov/cgi-bin/household/brands?tbl=brands&a...

elementcollector1 - 29-8-2012 at 21:29

Does that mean I will not be able to make potassium metal after all?
And what of distillation?

Wizzard - 29-8-2012 at 21:44

Heating over a temperature controlled hot plate in an RBF with a large watercooled condensor, coping to evaporate more tbutyl than water, then repeat the process to get a usable amount.

Rogeryermaw - 30-8-2012 at 03:34

http://hpd.nlm.nih.gov/cgi-bin/household/brands?tbl=chem&...

from the same site as the msds wizzard found, the other products by the same company that contain t-butanol all fall in at under 5%. the percentage in the octane booster is not even listed. i'm not saying that it is not possible but that it may not be a viable route. at any rate, many of us would love to have a reliable source of it so good luck and let us know what happens.

Squall181 - 30-8-2012 at 09:25

Is there any practical way to take T-butyl ether and make T-butanol form it?

T-butyl ether is found in a OTC product called start your engines.

Wizzard - 30-8-2012 at 09:54

Looks like it's MBTE, which is found in a few products. "Start your Engines" contains from 0-60% of it, by an MSDS I'm reading now.

"Methyl tert-butyl ether (MTBE) degradation by ferrous ion-activated persulfate oxidation: feasibility and kinetics studies."
http://www.ncbi.nlm.nih.gov/pubmed/19691249

elementcollector1 - 30-8-2012 at 17:00

Is there any way to turn MTBE into T-butanol?

hames - 31-8-2012 at 20:07

I have almost pure tert-butanol which freezes in the refrigerator but doesn't seem to freeze specifically at temps under 25 degrees unless refrigerated,I'm not sure the exact purity but I'm guessing its over 95% because it all freezes and there's no liquid left over.
Anyways as most people want it for a catalyst for the synthesis of potassium I'm willing to help fellow aussies out who seem to be having a hard time obtaining it,I have a bit over a litre of it and I'd be willing to flog off a few 100ml bottles or swap for some other reagents if anyones interested.

cheers jim

Dave Angel - 1-9-2012 at 02:03

Quote: Originally posted by elementcollector1

Is there any way to turn MTBE into T-butanol?

The attached paper describes the (albeit, undesired) acid catalysed hydrolysis of the ether.

Attachment: McLoughlin et. al. MTBE hydrolysis.pdf (136kB)
This file has been downloaded 939 times

Although this work was performed with low concentrations (that of potential ground water samples) it would seem that HCl is quite capable of effecting the conversion to TBA.

Rate of hydrolysis reported as 1.22/h at pH = 1 and 80 °C

Might be worth some experimentation if MTBE is more readily available than TBA.

Additionally, wikipedia describes HBr and HI as more effective catalysts for ether cleavage.

sbbspartan - 1-9-2012 at 10:26

From reading several MSDS sheets for "Start Your Engines", it appears that it contains 3 chemicals. <a href="http://www.hardwarestore.com/media/msds/126434.pdf">MSDS.</a>

Isopropanol - 0% to 20%
Xylene - 0% to 20%
T-Butyl Methyl Ether (MTBE) - 0% to 60%

I'm not the best chemist, but these could be fairly easily separated by simple or fractional distillation, right. Wikipedia (Yes, I know wiki isn't the best source of info) says that Isopropanol boils at 82.5 C and Xylene boils at 140 C, while MTBE boils at only 55 C. These would be fairly easy to seperate I think.

Then hopefully, you could use HCl for 'acid catalysed hydrolysis' of the MTBE. This forms Tertiary Butanol and Methanol according to <a href="http://iav.broadbrushart.com/Douthitetal2002.pdf">This PDF.</a>

Here is the formula - C5H12O (MTBE) + H2O ---> C4H10O (TBA) + CH3OH

From here you could separate them out through distillation (methanol boils at 65C and T-Butanol at 82C), or through cooling down(since t-butanol freezes at around 25C).

Would this work? I haven't been doing chemistry for very long so if this is has no chance of working just tell me. Would you even have to separate out the MTBE from the other chemicals, or could you just add HCl direct to the mixture, then separate T-Butyl based on freezing point or something like that? If it would work, that would be awesome since "Start Your Engine" is very readily available. Walmart carries it, as well as some local hardware stores. Its fairly expensive at around $7 for 4 ounces, but if you only need a little its not bad. I might go buy some and try this later, but right now I am pretty busy. Here comes some Potassium.

Lambda-Eyde - 1-9-2012 at 10:38

The isopropanol could maybe be removed by shaking with water. Some of the MTBE will be carried over, too. Anyways, if you only want to get the MTBE out, fractional distillation with a short column should be facile.

I doubt MTBE can be hydrolyzed with HCl, HBr or HI without converting the t-butanol to the halide or even giving isobutene. Preparation of t-butyl chloride is done by shaking t-butanol with aqueous HCl and leaving it for ~30 minutes or so IIRC. Cleaving the ether and preserving the t-butanol must be done with a non-nucleophilic reagent and a reagent that won't dehydrate the t-butanol.

[Edited on 1-9-2012 by Lambda-Eyde]

elementcollector1 - 2-9-2012 at 20:56

So... any suggestions for that non-nucleophilic reagent that can cleave MTBE for tert-butanol?

Dave Angel - 3-9-2012 at 09:50

Whilst HX may result in the tertiary haloalkane, it might be worth some experiments. I would not immediately rule it out on (albeit, educated) speculation, unless we have some literature to the contrary. What about dilute H₂SO₄ under mild conditions (to favor substitution)?

In addition to straight hydrolysis to TBA, I'd also be inclined to try for deliberate formation of the haloalkane, and then react with dilute, aqueous NaOH at low temperatures over a long time, again, to favor TBA (substitution product) rather than isobutene (elimination product).

I realise the tertiary nature of the species is a driver towards elimination, but I still feel that there's no harm in trying a few conditions rather than ruling these entire routes out. Even if the yield is low (say 20 %), with enough starting material, one could isolate a small quantity of TBA for potassium production.

Wizzard (or anyone else for that matter) you don't happen to have a pdf of the paper you linked to do you? (Water Environ Res. 2009 Jul;81(7):687-94) - persulfate route also appeals given OTC availability.

Would also like to add this project to my list; any joy with a UK OTC source of MTBE anyone?

jon - 8-9-2012 at 09:18

you know since hcl is such a poor leaving group you might have some success with that to yeild the chloride if you use accelerators like bromide or lithium chloride salts and lowered concentrations and temperatures as these accelerators allow one to do.
i.e. milder conditions aloowing for both kinetic and thermodynamic control of this reaction.
just a hunch, expiriment is king.
with the chloride in hand it's a simple matter of boiling in water to reclaimm the alcohol.
said alcohol would have to be dry dry dry to get sucessful results in making Kt-buto

[Edited on 8-9-2012 by jon]

jon - 8-9-2012 at 09:20

oh and just buy some mbte next time it's not hard to find

Dave Angel - 8-9-2012 at 13:31

Quote: Originally posted by jon

oh and just buy some mbte next time it's not hard to find

In that case, would you mind posting some examples of which types of stores / in what types of products (brands definitely useful) you've been able to locate MTBE for sale either in your OTC shopping experiences, or which sites you have found it freely available to the public online? I'm sure many of us would find this information to be a useful addition to the thread as, without the starting material, we're not doing any experiments!

jon - 8-9-2012 at 22:03

elemental scientific has mtbe
also try chemsavers.
elemental was formerly hagenow laboratories and is very open to individuals purchasing so is chemsavers.

hyfalcon - 9-9-2012 at 05:09

Apparently, at least in the registration FAQ, this company allows individuals to register. Check it out:

https://store.schoolspecialty.com/OA_HTML/ibeCCtpItmDspRte.j...

or:

http://compare.ebay.com/like/320945330818?var=lv&ltyp=Al...

[Edited on 9-9-2012 by hyfalcon]

Dave Angel - 28-9-2012 at 16:10

Quote: Originally posted by Dave Angel

Wizzard (or anyone else for that matter) you don't happen to have a pdf of the paper you linked to do you? (Water Environ Res. 2009 Jul;81(7):687-94) - persulfate route also appeals given OTC availability.

I've managed to get a copy of the persulphate paper. Apologies for the poor quality and size of the scan, I was in a rush when I photocopied it (I don't have access to neat electronic copies of journals, sadly):

Attachment: Chen et. al.pdf (1.1MB)
This file has been downloaded 923 times

To summarise, it seems that MTBE is indeed broken down by activated persulphate, however the resultant TBA is subsequently, itself, broken down further, so isolating the alcohol from a reaction mix using this process would be the challenge. In a batch process, work would be require to identify exactly what conditions to use and where to stop the reaction to maximise yield.

I'm still yet to identify an OTC source of MTBE in the UK, so no in-lab progress on this from me for the moment.

elementcollector1 - 28-9-2012 at 18:30

Distill the mix so that tert-butanol carries over as a gas, driving the reaction to the right? use molar amounts of persulfate and MTBE? Just a few guesses...

Nicodem - 29-9-2012 at 00:35

Quote: Originally posted by elementcollector1

So... any suggestions for that non-nucleophilic reagent that can cleave MTBE for tert-butanol?

I trully don't know what to think of a person who invests enough effort to make at least 4 replies on this topic, yet obstinately refuses to UTFSE.

UTFSE!

Dave Angel - 29-9-2012 at 00:49

Quote: Originally posted by elementcollector1

Distill the mix so that tert-butanol carries over as a gas, driving the reaction to the right? use molar amounts of persulfate and MTBE? Just a few guesses...

Perfectly good guesses, however with stoichiometric amounts, as soon as some TBA is formed, the persulphate will start acting on it as well as the MTBE. We end up with a mix of unreacted MTBE, TBA, and products of the decomposition of TBA - any CO<sub>2</sub> evolution likely to drive the reaction of TBA.

In removing the TBA, as it forms, by distillation the difficulty encounterd would be that TBA boils at 82 °C and MTBE at 55 °C - a high enough temperature to remove the product will also remove the starting material.

A possibility would be to use a hot, aqueous persulphate reaction mix and slowly drip the MTBE into it, allowing it to react and quickly distill off in very small amounts. In my thought experiment, this gives the MTBE time to convert to TBA but not much time for the TBA to further decompose. Some MTBE is still carried over, but so long as TBA isn't further degraded the product could be separated and the MTBE reused.

elementcollector1 - 29-9-2012 at 09:27

Quote: Originally posted by Nicodem

Quote: Originally posted by elementcollector1

So... any suggestions for that non-nucleophilic reagent that can cleave MTBE for tert-butanol?

I trully don't know what to think of a person who invests enough effort to make at least 4 replies on this topic, yet obstinately refuses to UTFSE.

UTFSE!

Tried. Got similar threads as this, with no suggestions whatsoever on cleaving MTBE. Any search terms I might be missing?

As for the persulfate bath, that seems a little tricky. There would probably still be some unreacted MTBE in the mix from vapor, but this could be removed by simple distillation.

Nicodem - 29-9-2012 at 23:04

Quote: Originally posted by elementcollector1

Tried. Got similar threads as this, with no suggestions whatsoever on cleaving MTBE. Any search terms I might be missing?

You might want to try investing more than just a couple of seconds in doing the search:
https://www.sciencemadness.org/whisper/viewthread.php?tid=11...

elementcollector1 - 22-11-2012 at 21:12

Idea!
Drip persulfate into a very cold solution of pure MTBE. Tert-butanol will freeze out.