Mercedesbenzene
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2-methyl-3-butyn-2-ol
I am looking into preparing 2-methyl-3-butyn-2-ol or dimethylethynylcarbinol. I want to attempt to synthesize this from calcium carbide, potassium
hydroxide and acetone as by Kazarian in 1934. I found the reference to his article from the organic synthesis article dimethylethynylcarbinol.
However, I have not been able to find the article yet, only references to it. I was wondering if anyone else had any experience in preparing this
compound or has this article. I am planning to finely powder the calcium carbide and potassium hydroxide and mix them in an equal molar quantity then
suspend the particles in an inert solvent and slowly add acetone. Then workup the product by quenching, extracting then distilling the product. I
found a very basic reaction mechanism here:
http://archive.org/details/organicsemi38391univ on page 80.
Anyone have thoughts on this reaction and reaction conditions?
[Edited on 27-11-2012 by Mercedesbenzene]
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Lambda-Eyde
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The article you're referring to appears in J. Gen. Chem. U.S.S.R., so it is most likely (>99%) in Russian. If you still think it could be of use to
you I could do a SciFinder search (provided you haven't done so yourself) later today.
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Mercedesbenzene
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I haven't yet done a Scifinder search. I might be able to get some useful information out of the article from a) google translate or b) someone who
speaks russian. If it indeed is in russian
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ScienceSquirrel
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I am not sure that your synthesis of ethynyl potassium would work, there is a preparation of it here;
http://link.springer.com/article/10.1007%2FBF01083799?LI=tru...
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Mercedesbenzene
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Hm. Thats true. However, I have the reagents so I will be trying to see if it works when exams are done in two weeks from now. I will let you guys
know if it works or not. If not I might go the lithium or sodium acetylide route as there are many available procedues out there.
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DJF90
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Acetylenes can be deprotonated using KOH/MeOH. I dont know how acetylene itself will hold up; I suspect you'll only get the monoanion but this is what
you want! I can vouch for this working with Phenylacetylene.
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ScienceSquirrel
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You could try adding calcium carbide to a solution of potassium hydroxide in methanol and then adding acetone.
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Nicodem
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The simplest methods rely on the addition of acetylene on acetone in DMSO using KOH as the catalyst (KOH in DMSO is more basic than the monopotassium
acetylide). See DOI: 10.1007/s11178-005-0331-7 for an example. See also DOI: 10.1002/jlac.198219820916 for another method using PTC conditions with
15% NaOH(aq) and toluene.
That journal has an English translated version that runs in parallel to the Russian one (but I did not check if the English translation goes as far
back as 1934). It is a common journal, so it should not be difficult to find it in the libraries or via interlibrary exchange (or via References
request). If one can't find the original article, the reactions applying the direct use of calcium carbide are reviewed in DOI: 10.1021/cr60065a006.
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Mercedesbenzene
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That's a very interesting paper Nicodem. I will most try this method next. I tried the calcium carbide, potassium hydroxide and acetone method. I
suspended fine powders of calcium carbide and potassium hydroxide in a some ether. I heated the mixture and nothing happened. I added the acetone and
left to reflux while I had dinner. I came back to find that the colour had changed from brown to green and the mixture had become very thick. I worked
up the mixture. There was a strong metallic garlic smell present after quenching with water. I presumed this to be phosphine and other noxious
impurities so this step was done in the fumehood. After extracting the aqeuous layer with ether I dried and filtered the resulting solution which was
green in colour. I didn't have time to purify it so that will be done next week. I plan to remove the ether on a water bath and purify the resulting
liquid by column chromatography as the amount of obtained produced is expected to be small. I worked on a 0.1 molar scale. I hope the KOH and DMSO
method works better as I don't fancy working with phosphine which results from impure calcium carbide.
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Lambda-Eyde
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Quote: Originally posted by Lambda-Eyde  | | If you still think it could be of use to you I could do a SciFinder search (provided you haven't done so yourself) later today.
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"Later" and "today" are both relative terms, right?
The SciFinder search didn't turn up anything, and I can't find it anywhere else, so I guess it hasn't been digitalized. I asked at the university
library, but they didn't have any volumes from earlier than 1949. I'll see if I can track it down somewhere else and order a digital copy of the
article.
Edit: Oh, and the conversation with the (young and new) clerk at the library was pretty funny:
Me: Hey
Her: Hi, can I help you?
Me: Um, yeah... I'm looking for... The Soviet Journal of General Chemistry?
Her: Okay, let's see here... Hm, which volume?
Me: Fourteen.
Her: Mhm. And what year?
Me: ... 1934
Her: Right.
Me: Right.
Her: You know, I don't think it's looking good for you...
Me: You don't say...
I doubt she gets such obscure requests every day. 
[Edited on 6-12-2012 by Lambda-Eyde]
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