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[*] posted on 12-12-2008 at 01:10
tert-Butyl Alcohol


I've looked around and have been unable to find any sort of OTC source or synthesis of tert-butyl alcohol.

I would imagine it could be had by cleavage of tert-butyl methyl ether, but I haven't seen a source of that either. Are there any other easily accessible compounds that have a tert-butyl that could be cleaved? I can't think of anything off the top of my head.

I could probably buy off the internet for $30-40/ 500ml but really would rather not.
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[*] posted on 12-12-2008 at 03:14


t-Butyl Alcohol should be easily obtained from a chemical supply house. Make some calls and ask if they are able to supply individuals. Some will and t-Butyl alcohol is not watched in any sense of the word and is not that dangerous either.

If you want to prepare it however it would be possible...

...Grignard!

Methyl Magnesium Halide + Acetone => t-Butyl alcohol

That is assuming you can find a source of acetone, methanol + some halogenating agent, magnesium, some form of drying agent etc. Easily doable I'm sure.




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[*] posted on 12-12-2008 at 03:23


Quote:
Originally posted by panziandi
Easily doable I'm sure.


Not sure if someone unable to acquire t-Butanol should attempt Grignards.




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[*] posted on 12-12-2008 at 05:04


Possibly true!



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[*] posted on 29-5-2011 at 17:41


Methyl t-butyl ether (MTBE) can be found in an auto store as an octane booster. I was in the store today and bought four cans (on sale for 99 cents each)! I got 1.5 liters of pure MTBE for 4 dollars!



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[*] posted on 29-5-2011 at 17:53


Meanwhile I recently checked several auto stores and found none. The capriciousness of chemical availability.



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[*] posted on 29-5-2011 at 17:54


I too have looked around for quite a while for t-BuOH with no luck and considered opening a thread on it, so I'm glad to see one open. When I looked into it a grignard reaction seemed like the best way to make it at home (though grignards are very difficult to do). It was really expensive and hard to find online.



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[*] posted on 29-5-2011 at 19:27


Wow MTBE! Extraction solvent. If you really wanted t-butanol you could reflux this with HBr to remove the methyl ether. Then you get t-butyl bromide, reflux with NaOH or something.

We are talking about tert-butanol and 2-methyl-2-butanol in the Make Potassium thread as well




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[*] posted on 30-5-2011 at 00:26


Quote: Originally posted by mr.crow  
Wow MTBE! Extraction solvent. If you really wanted t-butanol you could reflux this with HBr to remove the methyl ether. Then you get t-butyl bromide, reflux with NaOH or something.

Reaction of NaOH with t-butyl bromide (or chloride) gives isobutene, a useful compound, but a gas at room temperature. t-Butyl halides form mainly t-butanol upon solvolysis in water with acetone as cosolvent (a typical SN1 reaction thought to students and an lab exercise in kinetics). Not much of a prospect for preparative use, but might be an interesting experience in separation techniques.

Otherwise, MTBE can be cleaved directly to a mixture of methanol, t-BuOH and isobutene by dilute aq. non-nucleophilic acid catalysis (e.g., H2SO4, NaHSO4, etc.). The scientific literature is full of studies in this regard, but the preparative methods are mostly described in the patent literature.

MTBE reacts already with HCl, no need to use HBr. Essentially, MTBE can be used instead of t-BuOH in most SN1 reactions.
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[*] posted on 30-5-2011 at 07:49


Quote: Originally posted by Nicodem  

MTBE reacts already with HCl, no need to use HBr. Essentially, MTBE can be used instead of t-BuOH in most SN1 reactions.


@ Nicodem

(CH3)3.C.O.CH3 + 2HCl ------> (CH3)3CCl + CH3Cl + H2O

Is this what you are implying?

If yes then can it be done with aqueous HCl - say 30 % ?

Can you please site a preparative reference?

gsd
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[*] posted on 30-5-2011 at 08:25


Quote: Originally posted by Nicodem  
Quote: Originally posted by mr.crow  
Wow MTBE! Extraction solvent. If you really wanted t-butanol you could reflux this with HBr to remove the methyl ether. Then you get t-butyl bromide, reflux with NaOH or something.

Reaction of NaOH with t-butyl bromide (or chloride) gives isobutene, a useful compound, but a gas at room temperature. t-Butyl halides form mainly t-butanol upon solvolysis in water with acetone as cosolvent (a typical SN1 reaction thought to students and an lab exercise in kinetics). Not much of a prospect for preparative use, but might be an interesting experience in separation techniques.

Otherwise, MTBE can be cleaved directly to a mixture of methanol, t-BuOH and isobutene by dilute aq. non-nucleophilic acid catalysis (e.g., H2SO4, NaHSO4, etc.). The scientific literature is full of studies in this regard, but the preparative methods are mostly described in the patent literature.

MTBE reacts already with HCl, no need to use HBr. Essentially, MTBE can be used instead of t-BuOH in most SN1 reactions.


Thanks Nicodem, didn't know that about tert alcohols and ethers




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[*] posted on 30-5-2011 at 10:57


Contrary to what some have said it is extremely difficult, for some strange reason, to find t-butanol. Methyl t-butyl ether (MTBE) is, however, very easy to find so that is always an option.

If anyone needs a source for ACS Reagent MTBE online I know of at least one: about 500 mL for $20.




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[*] posted on 2-6-2011 at 06:53


Yesterday, in passing, I saw a hand sanitizer that contained T-butanol. a msds google search lists several that do.

I don't imagine it would be easy to separate from the other alcohols it's commonly mixed with...

2-Butoxyethanol Can be obtained as whiteboard cleaner, if that helps.
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[*] posted on 3-6-2011 at 17:13


I fail to see how 2-butoxyethanol has anything to do with t-butanol. Thanks for the info (it is quite common in a variety of cleaning solvents) but I just don't understand.

I think the main reason people seek t-butanol is, not because it is a 4-carbon, saturated alcohol but, because it is a tertiary alcohol. That is why 2-butoxyethanol is useless to people seeking it for that purpose.

But I see no reason why it shouldn't be mentioned--it would be bad to post that info in a new thread I guess.




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[*] posted on 4-6-2011 at 13:25


:( I thought I saw it in the thread, I must have had a brain fart.
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[*] posted on 5-6-2011 at 02:24


Quote: Originally posted by gsd  
@ Nicodem

(CH3)3.C.O.CH3 + 2HCl ------> (CH3)3CCl + CH3Cl + H2O

Is this what you are implying?

If yes then can it be done with aqueous HCl - say 30 % ?

Can you please site a preparative reference?

gsd

The general SN1 substitutions of MTBE go like this (where HNu is the nucleophile):

tBu-O-Me + HNu ---(acid catalysis)---> tBuNu + MeOH

In the case of HNu = HCl:

tBu-O-Me + HCl -----> tBuCl + MeOH

Since methanol is a primary alcohol, it can not undergo SN1 reactions, though it can react under the same conditions in other ways, depending on the conditions and nature of the nucleophile and catalyst (e.g., if HNu is CH3COOH, then it can obviously get esterified, while if HNu is HI it can undergo SN2 substitution to yield methyl iodide, etc.).

A very good article describing various SN1 reactions of tBuOH, its ethers and acid catalysed reactions of other aliphatic ethers is:
J. Am. Chem. Soc., 54 (1932) 2088–2100 (DOI: 10.1021/ja01344a062). A few excerpts:
Quote:
When tert.-butyl ethyl ether and concentrated hydrochloric acid in the molecular ratio of one of the former to five of the latter are mixed the ether dissolves, but is rapidly converted into tert.-butyl chloride, which separates. When such a mixture was allowed to stand overnight 99% of the theoretical quantity of the chloride was obtained.
...
There was an induction time before the chlorides separated. In order to have the results comparable zero time was taken when a measurable amount of chloride had separated-1 to 3% of the theoretical amount.
...
The tertiary butyl ethers react so rapidly with concentrated hydrochloric acid at 25 °C that it was necessary to study them under different conditions.

When applying this reaction on MTBE, using a mol ratio 10 : 1 of 27% HCl(aq) vs. MTBE, the reaction reached 25% conversion in 3.5 hours at 0 °C (while ethyl t-butyl ether required only 0.83 hours and t-BuOH 1.6 hours). So the reactivity MTBE in this chlorination is twice less than that of t-BuOH, but still relatively fast and obviously very fast at room temperature.

PS: In context of another thread an advice for those that have no distillation apparatus: N-(t-butyl)acetamide is a solid at room temperature (mp 96-98°C). So, if you wander what else you can do with MTBE, do this using the Ritter reaction on acetonitrile. If you have no acetonitrile, you can use urea as the nucleophile (the patent number for Ritter reactions using urea is already posted in some other thread).




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[*] posted on 5-6-2011 at 06:32


@Nicodem

Thanks for the very detailed reply. The JACS paper is very interesting indeed.

The preparation of tBuCl from tBuOH and aqHCl is a very basic reaction one encounters in Organic Syntheses. However as anyone who has actually performed this procedure can tell, any significant yields are realized only when a) A very large excess of HCl is used or b) when the product is "salted out" of the reaction mixture by inorganic salts like CaCl2 or ZnCl2 etc.

In case of tBuCl preparation using MTBE and aqHCl will the same principle hold good? Here the matter is further complicated by presence of Methanol in aqueous phase.

gsd
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[*] posted on 5-6-2011 at 13:10


I wouldn't know, as I never performed the reaction myself. t-Butyl chloride should not have much of a solubility in aq. HCl and the fact that in the article they obtain a 99% yield with ethyl t-butyl ether which cleaves to ethanol (a better cosolvent than methanol), can only mean the solubility can not be much of an issue (or perhaps they just got an impure product, or maybe it was due to the 5-fold excess of HCl and overnight reaction time?).

The Org. Synth. note about the addition of CaCl2 giving a better yield due to salting out the product might also be an misinterpretation of the practical results. It could be that with a just 3-fold excess of HCl and 15-20 min is not enough to achieve full conversion. In such case the addition of CaCl2 would indeed drive the reaction to completion by increasing the chloride concentration and reducing the free [H2O] content. Since the additionally formed product phases out, it might wrongly appear as salting out the dissolved tBuCl, while in reality it is just converting the dissolved tBuOH to tBuCl.

Chances are the Org. Synth. procedure wasn't really optimized. Or it could be optimized only on the economical base, as it gives a cheap reagent (tBuCl) from another cheap reagent (tBuOH), but uses a severalfold excess of another cheap reagent (conc. HCl). So the economic optimal might not be using even more HCl, as it would be when starting from an expensive alcohol to give an expensive chloride.




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[*] posted on 7-6-2011 at 08:53


Quote: Originally posted by 497  
I've looked around and have been unable to find any sort of OTC source or synthesis of tert-butyl alcohol.

I would imagine it could be had by cleavage of tert-butyl methyl ether, but I haven't seen a source of that either. Are there any other easily accessible compounds that have a tert-butyl that could be cleaved? I can't think of anything off the top of my head.

I could probably buy off the internet for $30-40/ 500ml but really would rather not.

Ullmann's 5th sez —

2-Methy-2-propanol ...

In the literature a number of other methods for the preparation
of butanol are cited which are generally of no significance other
than for laboratory preparation. A comprehensive review is to
be found in ....

B Cornils & E Zilly
Methodicum chimicum: a critical survey of proven methods and their application in chemistry, natural science, and medicine.
Vol. 5 (1975) p. 84

Byda Ullmann also notes that — prod. of propylene oxide yields
one ton per 1.2 t of propylene oxide. Must be a SL of it out there.

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[*] posted on 4-11-2011 at 09:26


This page
http://www.fuel-testers.com/review_gas_treatment_products.ht...

Lists "Turbo Octane Boost 180" which claims T-Butanol and methanol as the ingredients

While
http://www.chemcas.com/msds112/cas/1666/124-38-9_75-65-0_106...

Lists a brake cleaner composed of
"carbon dioxide
tert-butyl alcohol, tert-butanol
1,2-butylene oxide
methylal (dimethoxymethane)
perchloroethylene (tetrachloroethylene)
methyl chloroform"


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[*] posted on 5-11-2011 at 12:50


So I found some octane booster(Spectrum Plus @ K-mart) that is made with methyl-t-butyl ether. So i decided to buy and try to distill the ether off. I set up for basic distillation and turned on the heat. To my surprise the liquid is refusing to boil. So after a while I decided to take the temp of the liquid, while the still head was reading 30C the liquid in the flask was at about 120C. Unfortunately I was unable to locate an MSDS for this product.

Does anyone have any ideas on what's happening here, what other ingredient could be increasing the boiling point of the liquid. I'm about ready to give up on trying to make it boil.
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[*] posted on 11-11-2011 at 16:07


Quote: Originally posted by Nicodem  


Otherwise, MTBE can be cleaved directly to a mixture of methanol, t-BuOH and isobutene by dilute aq. non-nucleophilic acid catalysis (e.g., H2SO4, NaHSO4, etc.)


If this cleavage was done, would one separate the t-BuOH from the rest by cooling it? The t-BuOH would crystalize and the rest cold be poured off right?




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[*] posted on 14-11-2011 at 14:08


Quote: Originally posted by Takron  


If this cleavage was done, would one separate the t-BuOH from the rest by cooling it? The t-BuOH would crystalize and the rest cold be poured off right?


The t-butanol may not freeze into pure crystals from a mixture of solvents. While it readily freezes when pure, once you mix several liquids together, it is much harder to remove one by freezing it. Distilling them would likely work much better, then you could certainly freeze the crude t-BuOH distillate to try to repurify it by crystallization, and then pour off the non-solid material once ~90% has frozen.
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[*] posted on 19-11-2011 at 06:37


I don't get it. Carolina Biological------ 500ml -----$12.95

http://www.carolina.com/p2p/endecaSearch.do?pageName=Home+Pa...
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[*] posted on 19-11-2011 at 07:35


Quote: Originally posted by shadow  
I don't get it. Carolina Biological------ 500ml -----$12.95

http://www.carolina.com/p2p/endecaSearch.do?pageName=Home+Page&keyword=tert+butyl+alcohol&Search.x=0&Search.y=0[/url]

Quote:
Orders for hazardous materials (and kits and sets containing these items) can only be accepted from schools, research institutions, medical facilities, and businesses. Hazardous materials cannot be shipped to individuals, homeschoolers, and other customers.


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