Sciencemadness Discussion Board

Experiments with Vanillin and Ethyl Vanillin Ideas

Vicarious3rdEye2 - 7-3-2018 at 15:11

Hello everyone!

I don't know if this is the best place on the forum to post this but I have been at some sort of a chemistry version of "writers block" when it comes to experiments with Vanillin and Ethyl Vanillin.

I have a good amount (~ 100 grams) of each respectively and have nitrated vanillin on the 5 position and made 5-iodo Vanillin and Ethyl Vanillin since those syntheses are widely available on the internet mostly on this forum.

I find these two compounds very interesting and it is a very good way for me to challenge my knowledge of organic chemistry as well as just have a good time doing it.

But I have had some trouble coming up with any more ideas of reactions I can do with said compounds. I know it might just be best to walk away from it and wait for an idea to come to me at another time but I thought I would ask.


Anyone know any interesting reactions with either of these compounds?

I have a pretty vast amount a reagents at hand so I am open to any ideas.

I hope this is appropriate, I am not asking to be spoon fed anything just looking for ideas to be thrown around. Even something you could call exotic.

So far the only things I could think of would be oxidizing the aldehyde to the carboxylic acid and making esters, or converting the Iodo- groups into hydroxyl groups but I know that 5-hydroxy Vanillin has been discussed to death on this forum and I have not had any luck trying to produce that compound.

Again I apologize if this post isn't appropriate, please say so if this is not good posting practice.

j_sum1 - 7-3-2018 at 15:25

Here's a start...
https://www.youtube.com/channel/UCiU1dHvZObB2iP6xkJ__Icw/sea...

Vicarious3rdEye2 - 7-3-2018 at 17:40

Thank you j_sum. I have seen every Chemplayer Video they have done on Vanillin and probably 65% of all their other videos and they have amazing stuff, I am a big fan. I don't have any Nitromethane to perfirm the Henry reaction or the others they did that require NM but I was more asking for reaction ideas that haven't really been done too much and/or that is lacking in the literature. I was thinking of coming up with my own hypothesis for a reaction and then carry it out and post my results for discussion.


Maybe I should just wait to post until I actually have something to talk about instead of asking for ideas. I just wondered if anyone had any interesting ideas of their own outside of what has been done before by anyone on this forum that they would be curious of seeing what the results were.

j_sum1 - 7-3-2018 at 18:55

I think chemplayer's attraction was that vanillin is simultaneously an aromatic hydroxide, an ether and an aldehyde (although I think it was the latter that was most appealing). As such it can act as the substrate in a wide range of reactions. IOW, go with a standard idea and see how it goes on vanillin.

(Only 65%?? I think I am sitting at 180% having watched everything at least once and most twice.)

The Volatile Chemist - 7-3-2018 at 20:44

Chemplayer is like a really good TV show you have to re-watch.

As far as vanillin reactions go, chemx01 has some vanillin reactions:
https://www.youtube.com/user/chemx01/videos

There are a lot of cool condensations you can do with aldehydes. Besides those with alkyl nitrates, it condenses with acetone (and other ketones) from what I understand.

DJF90 - 8-3-2018 at 00:55

Theres also this: http://www.sciencemadness.org/talk/viewthread.php?tid=23431

DraconicAcid - 8-3-2018 at 01:04

You can oxidize it to vanillic acid, and make esters.

Boffis - 8-3-2018 at 07:14

You can fuse it with KOH and prepare 3,4-dihydroxybenzoic acid (pyrocatechuic acid), reduce it with NaBH4 to vanillyl alcohol or oxidize it with silver oxide to vanillic acid.

You can nitrate vanillin to 5 nitrovaillin with nitric acid or you can nitrate it with silver nitrate to yield 5-nitrovanillic acid and or vanillic acid depending on the condition (see I A Pearl; JACS; 1946, p1100).

It was the same author who did the silver oxide and some of the caustic fusion method work too. He did a lot of work derivatizing vanillin, his papers are worth checking out.

This paper from JofChemEd is interesting too.

Attachment: dSkgxklzc (2MB)
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[Edited on 8-3-2018 by Boffis]

[Edited on 8-3-2018 by Boffis]

Pumukli - 8-3-2018 at 12:22

Condensation reactions with ketones. With simple acetone it is good, but even better with acetylacetone (if you have some). As I remember it should give something closely resembling to zingeron or what.
There are other strongly bioactive compounds with a vanilline building-block, but suggesting something like a nonivamide (or alike) synth might be too much.

Vicarious3rdEye2 - 8-3-2018 at 12:30

Yes j_sum I should be more honest, I have watched about 65% of Chemplayer's videos but with the ones I have watched I must of re-watched at least 10-20 times depending on the video lol.

I love those guys (and/or girls?)

Out of all of the wonderful chemistry channels they have a very special place in my heart and better than most movies I watch half the time haha.

Oh and thank you for the ideas DraconicAcid and Boffis I didn't even think about making the nitro product of the carboxylic acid!

And I had no idea I could use Ag2O as an oxidizing agent and AgNO3 for a nitration! These types of things were exactly what I was looking for, something I have never come across yet or at least come across and remembered. I don't have any Sodium Borohydride yet which is kinda funny as I have been able to source a good amount of rather harder to obtain (at least in terms of good price and purity) reagents like Ceric Ammonium Nitrate, P2O5, NaN3, NH2OH*HCl, 120mL of THF and DMF and stuff like that.

DraconicAcid - 8-3-2018 at 12:35

If you do the reduction to the alcohol, remember that benzyl alcohols are sensitive to acids. We did that as a first-year organic lab, once and the students read the directions to "place the sample in an ice bath, then carefully acidify to precipitate the product." For some reason, the twits decided that it didn't say anything about *leaving* the sample in the ice bath, and took it out before adding hydrochloric acid, thus forming a benzyl chloride and an intractable oil.

Vicarious3rdEye2 - 8-3-2018 at 12:35

I have been trying to fully understand how the cleavage of ethers work on aromatic aldehydes. I have only done chemistry for about two years on my own and have more reagents and glassware than knowledge at the moment so I think it is time to hit the textbooks.

Not to bring this off topic but I actually was really in need of some physical text books but not wanting to spend the money and I recently found out that my neighbor who I have only met twice has a Doctorate in Chemistry and said I could borrow any textbook from his school years anytime I want as well as ask him any questions about reactions I might have!

A very very pleasant surprise!

Vicarious3rdEye2 - 8-3-2018 at 12:38

Oh wow that sounds like a really unpleasant and dangerous situation.

I've only made Benzyl Chloride once in a very small quantity and didn't even finish the final purification stage because the vapor could be smelled (and felt) all the way three floors up in my house from where I was doing it in my basement.

I really need to build some sort of basic fume hood for when it's too cold outside to do reactions.

DraconicAcid - 8-3-2018 at 12:39

To be precise, it wasn't benzyl chloride itself, but "a" benzyl chloride- it still had the hydroxyl and methoxy substitutents on it, so it wasn't volatile. I guess it would be vanillyl chloride.

[Edited on 8-3-2018 by DraconicAcid]

Vicarious3rdEye2 - 8-3-2018 at 12:40

But thank you for the heads up Draconic it's always good to remember these sorts of things, chemistry mistakes can be very unforgiving *if* you are even lucky.

Vicarious3rdEye2 - 8-3-2018 at 12:41

Oh yes I see of coarse I didn't even think about that.

Vicarious3rdEye2 - 8-3-2018 at 12:45

That's what fascinates me though so much about Vanillin and Bourbonal is how many compounds can be made from it. I wish I could make a real go at 5-hydroxy Vanillin but it seems like there is always the use for Dimethyl Sulfate at some point which I am not qualified enough in my eyes to deal with. Actually I might be mistaken, maybe DMS is used for other benzaldehyde derivatives.

myristicinaldehyde - 8-3-2018 at 13:10

Quote: Originally posted by Vicarious3rdEye2  
That's what fascinates me though so much about Vanillin and Bourbonal is how many compounds can be made from it. I wish I could make a real go at 5-hydroxy Vanillin but it seems like there is always the use for Dimethyl Sulfate at some point which I am not qualified enough in my eyes to deal with. Actually I might be mistaken, maybe DMS is used for other benzaldehyde derivatives.


DMS is sued for the selective methylation to syringaldehyde (sp?). Using sodium methoxide on iodo or bromovanillin instead of sodium hydroxide should work if that's your goal. You don't need DMS for just 5-hydroxyvanillin.

Pumukli - 8-3-2018 at 13:17

Forget DMS or any other alkylating agents under your circumstances! Do more basic stuff with less volatile compounds! You gassed the house once, it can quickly bring an end to your "carreer" as amateur chemist! :-)

Vicarious3rdEye2 - 8-3-2018 at 14:02

Oh yeah I had that one accident and it was minor compared to many other things that could have gone wrong. I try to treat almost every reaction with the same respect you would with a firearm. Don't get careless and research before you go doing any reactions so you don't to anything that could result in a deadly accident.
I am not interested in winning a Darwin award. I don't want to be K3wl, I don't want to cook anything other than bacon and eggs, I don't want to be spoon fed because I am not a child (at least I would like to think so lol) and I am not interested in "Swimming" unless it's in a Lake in Maine.

I hope that's clear as I see too many new members post either very sketchy stuff or are asking questions that sound like the only knowledge they have is straight from the anarchist's cookbook or other bullshit book.



The most dangerous material I will handle at the moment is Sodium Azide and only in very small amounts with proper precautions set in place. With HCN at least it's supposed to smell like something (not that I would like to be in a position to learn that first hand) rather than HN3 which is completely odorless. Among many other things.



Vicarious3rdEye2 - 8-3-2018 at 14:17

Anyways I think I might give 5-Hydroxy Vanillin another go

I already have 5-iodo Vanillin and 5-Iodo Ethyl Vanillin which I would be interested in seeing the difference in product and how the reaction time varies.