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Author: Subject: Camphor reduction to borneol/isoborneol
12thealchemist
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[*] posted on 12-12-2018 at 05:25


Quote: Originally posted by stamasd  
Quote: Originally posted by 12thealchemist  
If you're doing NurdRage's sodium metal production reaction with borneol, it is possible that camphor may work, if a hypothesis of mine is correct. I hypothesise that it is the enolate that is the active catalyst, and borneol (or another secondary alcohol) is just a pre-catalyst. The enolate would be formed from the corresponding ketone via alpha-hydrogen elimination.


I know of one way of testing that hypothesis. :) But I need borneol for that. :D
(7 years of graduate school has taught me the importance of controls)


This is very true. However, since NurdRage has already tested borneol, it is not inconceivable that it would work under the slight modifications you would be using. On the other hand, it is better to do a small amount of good science than lots of bad science.




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stamasd
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[*] posted on 12-12-2018 at 17:33


One problem with using a shortcut would be, if it doesn't work I won't know if it's a problem with the reaction mechanism, or with my technique. I need a positive control, as close as possible.

[Edited on 13-12-2018 by stamasd]
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12thealchemist
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[*] posted on 13-12-2018 at 08:58


That is a very good point. Once you establish that you can replicate the reaction, while it would be interesting to see if camphor works, it is entirely up to you.



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stamasd
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[*] posted on 20-12-2018 at 14:50


So I received today the "borneol" I had ordered from India. What a surprise, it's not borneol. It's camphor. It looks like camphor, it smells like camphor; if I put this and a sample of camphor next to each other I cannot distinguish them by appearance or smell. Moreover the package it came in is labeled "camphor" and the invoice included has "camphor" handwritten. In a few days I'll have time to determine its MP and conclusively prove it's not borneol.

Scratch this source.
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Σldritch
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[*] posted on 21-12-2018 at 05:40


Dithionite reduces ketones to alcohols and can be bought as a reductant for indigo. The hard part would be choosing a suitable solvent.
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stamasd
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[*] posted on 21-12-2018 at 06:19


Quote: Originally posted by Σldritch  
Dithionite reduces ketones to alcohols and can be bought as a reductant for indigo. The hard part would be choosing a suitable solvent.


According to unionist's post on the first page it is known not to work for camphor.

I don't have dithionite (though I could get some easily) but I do have some amino(imino)methanesulfinic acid (AKA thiourea dioxide) and could try it sometime next week, when hopefully I will have some time to attempt the Urushibara reduction too. I assume an alcohol should be a suitable medium for the reaction.

[Edited on 21-12-2018 by stamasd]
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[*] posted on 21-12-2018 at 06:23


These
"known not to work" and
"The hard part would be choosing a suitable solvent."
May be two ways to say the same thing.

The paper I cited says it fails because the camphor sublimes out of the mixture.
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stamasd
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[*] posted on 21-12-2018 at 06:26


Quote: Originally posted by unionised  
These
"known not to work" and
"The hard part would be choosing a suitable solvent."
May be two ways to say the same thing.

The paper I cited says it fails because the camphor sublimes out of the mixture.


I agree, that's why I'm willing to try it.
Probably in a reflux setup so that the refluxing alcohol can bring back the sublimated reagent.

http://reag.paperplane.io/00002692.htm

[Edited on 21-12-2018 by stamasd]

[Edited on 21-12-2018 by stamasd]
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Σldritch
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[*] posted on 21-12-2018 at 15:53


Sorry i just skimmed through the thread and thought it was mostly about Sodium Borohydride. Having read it again i suggest you separate the borneol and camphor by simply polymerizing the ketone in alcoholic hydroxide for a while and then filter off the resulting crap and distill/sublimate out your product.

I was about to suggest Thiourea dioxide too until i opened that link last second. :P I think there is plenty of ways to reduce ketones to alcohols but i can not remember any more now.
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[*] posted on 7-1-2019 at 19:44


Ummm. Read Na procedures. Borneol worked the best .

Sadly, best online Camphor reduction procedures, explored so far, require Borohydride.

There are some Chinese patent postings... utilizing MPV, but they are more or less unintelligible.
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[*] posted on 7-1-2019 at 20:31


https://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/revie...

http://www.sciencemadness.org/talk/viewthread.php?tid=3151

Make some NaBH4

thankfully I have a bottle of distilled trymethelboride

[Edited on 8-1-2019 by XeonTheMGPony]
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[*] posted on 16-1-2019 at 18:51


Too good to be true?

https://www.jstor.org/stable/pdf/25138688.pdf
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[*] posted on 17-1-2019 at 01:25


Quote: Originally posted by icelake  
Too good to be true?

https://www.jstor.org/stable/pdf/25138688.pdf

Rather not.
Sodium in alcohol seems like very plausible way to reduce a ketone. However, we're using sodium to produce borneol to produce sodium ;)
So I think my idea from the first page of using Na-MgO aggregate is slightly more effort-effective.
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[*] posted on 17-1-2019 at 04:52


Quote: Originally posted by oberkarteufel  

However, we're using sodium to produce borneol to produce sodium ;)


True, but Nurdrage's method requires few grams of sodium jump start anyway (to protect Borosilicate glassware).
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[*] posted on 22-1-2019 at 19:05


Sodium borohydride is likely to be the easiest option by far.
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XeonTheMGPony
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[*] posted on 1-2-2019 at 19:11


https://www.youtube.com/watch?v=XxCIVTdXWQU
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[*] posted on 2-2-2019 at 00:00


Quote: Originally posted by XeonTheMGPony  
https://www.youtube.com/watch?v=XxCIVTdXWQU

Trust me - everyone truly interested in this topic has already seen this update ;)
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[*] posted on 2-2-2019 at 07:16


Gotta make sure! I been downloading every single one since you tube proved less then reliable stewards of knowledge.
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[*] posted on 4-2-2019 at 18:14


2 days? Hardly anyone had seen that update!

Thank you, Xeon.

So it seems, folks online, are claiming to be selling Borneol, but they aren't?
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[*] posted on 5-2-2019 at 11:07


zed

I found a seller on alibaba, "Shandong Look Chemical Co., Ltd". They seem legit, and I ordered borneol from them. Just some issues, first they have a minimum order size of 1kg, which is kind of a lot when you are using it as a catalyst for a hobby. Second, it is not cheap, cost me $200 including transport.

3rd, and most importantly, I cannot yet vouch 100% for the authenticity of the borneol. It does smell somewhat different from camphor, and the crystals are different, but testing the melting point turned out to be a bit tricky.

I made some 1,4-dioxane today (pending purification) and will let you know if I can recommend them as a supplier when I have time to go through all the remaining steps.. If I get the Na production going it will be a pretty definite confirmation that it is indeed borneol.
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[*] posted on 7-2-2019 at 11:49


Quote: Originally posted by stamasd  
So I received today the "borneol" I had ordered from India. What a surprise, it's not borneol. It's camphor. It looks like camphor, it smells like camphor; if I put this and a sample of camphor next to each other I cannot distinguish them by appearance or smell. Moreover the package it came in is labeled "camphor" and the invoice included has "camphor" handwritten. In a few days I'll have time to determine its MP and conclusively prove it's not borneol.

Scratch this source.


I had this exact same experience with "Borneol" from the Ping Jian (India) same seller. Same labeled invoice as camphor, and an explanation from the seller indicating it is borneol and that they use camphor as a name interchangeably.

Melting point was not crisp and I was not able to use MP to discern between the two. I noted that the density differences should have borneol heavier than water and camphor lighter than water. Distilled water, at exactly 20C and a small crystal carefully pushed beneath the surface (no clinging bubbles) slowly drifted up to the surface of the water.

I tried the half mole reaction with lithium as a jump start and was able to get product, however it took three days and an added addition of the 'borneol' catalyst at day 2.

A full mole run a few days later with both menthol and suspect "borneol" gave much better results and finished in a bit more than two days with better product.

Good Luck!
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