Sciencemadness Discussion Board
Not logged in [Login ]
Go To Bottom

Printable Version  
Author: Subject: Hydrogenation of Eugenol
semiconductive
Hazard to Others
***




Posts: 181
Registered: 12-2-2017
Location: Scappoose Oregon, USA.
Member Is Offline

Mood: Explorative

[*] posted on 1-11-2020 at 22:30
Hydrogenation of Eugenol


I've been looking at a reaction to make elemental sodium based on menthol that proceeds fairly slowly eg: 30 hours;

See the discussion about 20 minutes into this video:
https://www.youtube.com/watch?v=PxPjBz_8S3c

He compares menthol with Borneol, which is much more difficult to get and expensive.
But Eugenol is ubiquitous.

I was curious, Eugenol has the double carbon bonds that aromatics have and is likely more reactive than menthol. But I've seen several articles talking about converting Eugenol to a saturated hydrocarbon by use of ruthenium or other catalysts and high pressure hydrogen.

But my research shows nickel is likley just as effective ...

nickel sponge (raney nickel), is difficult to get ... but I can electroplate nickel onto graphite dust very easily. Several articles I've looked at have shown successful hydrogenation of aromatic rings using nickel powdered, or mixed with graphite; Apparently only speed of hydrogenation is affected by how spongey the catalyst is.

My expeience in organic chemistry is limited ....
but I saw, for example, an aromatic ring that I think was c6H6O3 (similar to phenol, but with 3 OH groups and not a saturated ring. ).

So, I was thinking ...
If I were to attempt to hydrogenate eugenol using hydrogen gas and a nickel catalyst, Which sites should I expect are more likely to hydrogenate easily and which ones would be more difficult?

Would the oxygen + methyl group on eugenol cleave and become an -OH ?
Would the double carbon bond on the hydrocarbon tail likely hydrogenate -- or is only the aromatic ring most susceptible to hydrogenation ?

why/why not?

Since I'd like to do this experiment ... could anyone suggest the minimum pressure and temperature I need to maintain to have a reasonable chance of success?





[Edited on 2-11-2020 by semiconductive]
View user's profile View All Posts By User
njl
National Hazard
****




Posts: 290
Registered: 26-11-2019
Member Is Offline

Mood: 20 miles into bat country

[*] posted on 2-11-2020 at 08:08


Working through your post sequentially:

1. Nurdrage is using menthol because it is a secondary alcohol that is easy to obtain and works as the catalyst in his reaction.
2. Eugenol will probably not work there.
3. He compares menthol to borneol because borneol is another widely available secondary alcohol.
4. Nickel sponge and Raney nickel are not the same.
5. The double bond in the allyl group will be hydrogenated.
6. No, the ether will not be cleaved.
7. The ring is much less prone to hydrogenation.
8. Catalytic hydrogenation is well documented already. You should be able to find conditions applicable to the hydrogenation of eugenol in existing literature.

Now, what does sodium production have to do with this? Eugenol, before or after hydrogenation, will probably not be an effective catalyst. Nurdrage discovering menthol as an effective catalyst is great because you can't really beat it in terms of accessibility and cost.
View user's profile View All Posts By User
zed
International Hazard
*****




Posts: 1920
Registered: 6-9-2008
Location: Great State of Jefferson, City of Portland
Member Is Offline

Mood: Semi-repentant Sith Lord

[*] posted on 3-11-2020 at 12:47


The hydrogenation/saturation of aromatic rings, is achieved with difficulty. Lots of pressure, special catalysts, etc, etc, etc..

Now, under some circumstances, ethers can be cleaved by hydrogenation. But, that trick is more easily performed on Benzyl Ethers. Notably, the technique is sometimes used in the synthesis of Psilocin.

Probably a better investment in time and money, to buy either Borneol or Menthol, and start from there.
View user's profile View All Posts By User
semiconductive
Hazard to Others
***




Posts: 181
Registered: 12-2-2017
Location: Scappoose Oregon, USA.
Member Is Offline

Mood: Explorative

[*] posted on 5-11-2020 at 10:24


Quote: Originally posted by njl  
Working through your post sequentially:

Now, what does sodium production have to do with this?



I do have Menthol. So, repeating nurdrage's experiment is not my major purpose nor is finding a better catalyst. I do experiments to learn and improve my chemistry knowledge.

In the video Nurdrage begins developing a scientific theory of why secondary and tertiary alcohols work in the reaction -- but primary alcohols do not. I found his reasoning extremely interesting.

The theory has to do with the size of the alcohol molecule near the -OH bond and it's ability to replace -O/ or -OH in a magnesium oxide crystal. Most of nurdrage's theory of what prevents incorperation is the 'nearness' of a radical to the -OH radical on the alcohol.

Primary alcohols, by definition ... don't have sites to 'widen' the molecule because the OH radiical generally appears on the end of a saturated chain. (n-hexanol, methanol, etc. )

From my knowledge of reactivity (see past threads); primary alcohols are the least chemically reactive, followed by secondary alcohols, and finally tertiary alcohols. This generalization was bolstered by organic chemistry texts I have read concerning fuel processing from the 1960's ( eg: college texts and lab books from the petrol industry in that time period in the U.S.A. )

So, nurdrage's theory is interesting (to me) because his theory fits with much of what I have learned in O-chem books I have access to in the local library. Nurdrage posits that any secondary alcohol ought to either produce a compete sodium conversion reaction or none at all. The catalyst efficiency doesn't really depend on the 'strength' of the -OH bond in secondary alcohols, because if it did ... the reaction would not work at all in many cases rather than work with reduced efficiency.

So, nurdrage positis an empirical criteria for selecting a secondary or tertiary alcohol based on the apparent width of the molecule near the OH bond.

Eugenol meets this criteria for physical width, although the -O- in the ether bond was something I thought might disqualify it from nurdrage's simple analysis.
But if the bond will not be cleaved (as you say), then Eugenol remains a single -OH radical alcohol even after hydrogenation.

Hydrogenation is simply to reduce the ractivity of the cyclic bonds and convert it to a saturated alcohol, similar to Menthol and Borneol.

So, his theory becomes testable with a substance that is only minorly different from the working catalysts.

Regarding Raney Nickel:
Only aluminum and nickel are required to make that catalyst. Other metals (promotors) are optional. According to wikipedia, the aluminaum is structural and not chemically active in the process. So, I think a pure nickel catalyst should still work as long as it has lots of surface area and some kind of support.

Graphite seems as good a support that would produce large amounts of nickel surface area with only a thin, inexpensive, coating of nickel. So it's worth trying to make a conductive nickel catalyst that way.

Several of the experiments I saw used pure nickel catalysists when converting Eugenol, so I don't think Raney nickel is critical to the process of hydrogenation.

Although I would expect many online literatures to give pressures and temperatures for hydrogenation, my initial search produced only closed shop documents that have to be purchased before getting details. My searches have not found summaries of articles which assure me the pressure ranges and temperatures are fully disclosed in the article. I hate buying an article only to find out it doesn't have the data after I wasted money .... I figured I'd ask here, first; since my first searches gave no definite article I could purchase with all the necessary data.

I can buy Raney nickel (un-etched) for reasonable prices. But, it's more work to leach the metal to make a fresh batch than electroplating is. (Aluminum after etching tends to be pyrophoric.) So I plan to try electroplated graphite first. It may not be as fast or reactive a catalyst as Raney nickel, but nickel dust should store for a long time without degradation. Such a nickel catalyst is probably also useful in fuel cell and battery experiments; so I have multiple ways to use the product.

Eg: A sodium-ion battery might be possible using a graphite-nickel catalyst. etc.
Such a battery would not be as efficient as lithium ion, but sodium and potasium are both extremely easy to get. Nurdrage's chemistry opens up new possibilities to explore for potassium or sodium based fuel cells and batteries.

View user's profile View All Posts By User
njl
National Hazard
****




Posts: 290
Registered: 26-11-2019
Member Is Offline

Mood: 20 miles into bat country

[*] posted on 5-11-2020 at 10:41


I have no idea what you are saying above the words "Regarding raney nickel" so I can't add on to that.

Raney nickel IS pure nickel (at least in theory). The aluminum is just part of the production process to make extremely fine nickel particles that can act as a heterogeneous catalyst. It is just unsupported, finely divided nickel. I think your idea for electroplating nickel on to graphite is neat and I would be interested in your results should you go through with the reaction. I don't know what experiments you're referring to, but "pure nickel" is almost certainly not the required catalyst. In addition to the metal itself, it must be fine enough to stay suspended in a reaction mixture and have enough surface area to pick up hydrogen at an appreciable rate. A lump of nickel will not work. Another support you could try is silica, where you first etch the SiO2, then deposit a nickel salt on the surface of the silica particles, and then reduce the nickel salt with hydrogen gas to form silica with nickel metal embedded in itself.
View user's profile View All Posts By User
zed
International Hazard
*****




Posts: 1920
Registered: 6-9-2008
Location: Great State of Jefferson, City of Portland
Member Is Offline

Mood: Semi-repentant Sith Lord

[*] posted on 8-11-2020 at 03:22


Oh, there are some decent Hydrogenation Books available on line, for free.

Also, such books are available for sale, at reasonable prices. Ebay, Advanced Book Exchange, ect..

I'll take a look.

OK, try our references section. Some hydrogenation links are still active. Do you have access to our references forum?

Sometimes very expensive books are available on trial. After a limited time, they evaporate from your computer. Though if your have an economical printer, you may be able to print yourself a binder copy, for your own use.

Organic Functional Group Hydrogenation
Robert L. Augustine

Oh, yeah.... This one ain't bad for 35 bucks. It's about a 300 dollar discount. https://www.ebay.com/itm/Handbook-of-Heterogeneous-Catalytic...

Rylander has a big rep, though I have sometimes seen them cheaper. https://www.ebay.com/itm/Catalytic-Hydrogenation-in-Org-Synt...

[Edited on 8-11-2020 by zed]

[Edited on 8-11-2020 by zed]

[Edited on 8-11-2020 by zed]
View user's profile View All Posts By User
Corrosive Joeseph
International Hazard
*****




Posts: 875
Registered: 17-5-2015
Location: The Other Place
Member Is Offline

Mood: Cyclic

[*] posted on 8-11-2020 at 05:23


'DIY Hydrogenation Resource' - https://www.sciencemadness.org/whisper/viewthread.php?tid=86...



/CJ




Being well adjusted to a sick society is no measure of one's mental health
View user's profile View All Posts By User
Opylation
Hazard to Self
**




Posts: 90
Registered: 30-8-2019
Member Is Offline


[*] posted on 8-11-2020 at 06:14


I’m pretty sure I heard somewhere nurdrage has a Ph. D in chemistry. He briefly went over the mechanism and his theory for those that were interested but if you’re not sure how to do simple reactions like hydrogenations then I wouldn’t dive deep into the theory of nurdrages process. What is your goal here? Is it a hydrogenation of Eugenol or to obtain sodium metal? If your goal is either then I would look up the process on how to do it and then have a shot at it. If you’re truly trying to understand the mechanism and theory behind why it works though, you’re really gonna need to work your way up to it. There are many many different concepts that tie into that sodium preparation that are not going to be able to be conveyed over a forum. It takes many years of studying chemistry, like Gibbs energy, ordered rates of reactions, steric hinderances, affinities, etc. to be able to truly understand what’s going on there. My advice is if you really want to be able to understand the mechanism and WHY something is happening in chemistry you got to develop the building blocks first. You gotta crawl before you can walk

[Edited on 8-11-2020 by Opylation]
View user's profile View All Posts By User
draculic acid69
International Hazard
*****




Posts: 992
Registered: 2-8-2018
Member Is Offline


[*] posted on 8-11-2020 at 18:01


Buying camphor and making borneol would be a much better idea.eugenol won't work well if at all for the sodium rxn.in the other nurdrage videos it explains the mechanism of the rxn and what works and what does not.also aromatic groups decomposed when used for the sodium rxn(but not potassium) and double bonds were also suspected of being a cause of decomposition of the catalyst
View user's profile View All Posts By User
nora_summers
Harmless
*




Posts: 34
Registered: 11-11-2010
Member Is Offline

Mood: I am figment of your imagination.

[*] posted on 9-11-2020 at 22:32


Quote: Originally posted by Corrosive Joeseph  
'DIY Hydrogenation Resource' - https://www.sciencemadness.org/whisper/viewthread.php?tid=86...



/CJ


Link doesn't work
View user's profile View All Posts By User
Corrosive Joeseph
International Hazard
*****




Posts: 875
Registered: 17-5-2015
Location: The Other Place
Member Is Offline

Mood: Cyclic

[*] posted on 9-11-2020 at 23:12


References sub-forum..... PM admin for access.


/CJ




Being well adjusted to a sick society is no measure of one's mental health
View user's profile View All Posts By User
zed
International Hazard
*****




Posts: 1920
Registered: 6-9-2008
Location: Great State of Jefferson, City of Portland
Member Is Offline

Mood: Semi-repentant Sith Lord

[*] posted on 12-11-2020 at 03:50


Personally, I just tried all of those links. I was only able to open a few of them.

It's a thing. They age out, pretty quickly.

Sorry about that Nishimura, that was for sale... dirt cheap.

I put it out there for a while. When nobody jumped on it, I bought it myself.
.........................................................................................

Nurdrage may have a Phd in Chemistry. Not unusual around here.

Though Nurdrage is actually more accomplished than many Phds.

I've known some guys outside, with Phds in Chemistry or Biochemistry....that would be lost here.

A few years, of regular interaction at SM.... broadens your
horizons.
.....................................................................................

As for actually obtaining experimental details, you either have to have an account that allows it, or you need library access.

Most college libraries have accounts that allow online access to the major chemistry journals; perhaps even hard copies of the journals themselves. Just walk in, and sit down at a computer station. Well, if they are open during the pandemic.

In recent years, I have utilized Portland State and Reed College.

Back in the day, we used to make the pilgrimage to U.C. Berkley. Wherein, once you got inside, you could stay inside.
Provided you got inside, before they locked-up for the night....you could stay there for days, if you wanted to.

Which, of course, is what you need to do, to succeed. Most articles, are dead ends.

.......................................................................................

Oh, it occurs to me, that it might be possible to achieve this Na reaction, utilizing a secondary amine. Perhaps the product of camphor.... reductively aminated with methyl amine?

Probably stinky though.
.......................................................................................

Oh, I notice you are in Scapoose. Call Portland State Library.

Walk in, ask to use the computers, as a guest. They usually give you access for an hour or two, per day. You can access articles online, and print them. Gotta pay for parking! Under current circumstances, don't be there after dark, or on a weekend. After dark, climatic conditions, may cause your car windows to explode.
[Edited on 12-11-2020 by zed]

[Edited on 12-11-2020 by zed]

[Edited on 12-11-2020 by zed]

[Edited on 12-11-2020 by zed]
View user's profile View All Posts By User
Bubbles
Harmless
*




Posts: 10
Registered: 13-7-2020
Member Is Offline


[*] posted on 12-11-2020 at 06:39


Yesterday I made (iso)borneol from camphor with sodium borohydride. Literally the easiest organic synthesis I ever performed, loved it.
View user's profile View All Posts By User

  Go To Top