Sciencemadness Discussion Board - Uses for salicylaldehyde

Uses for salicylaldehyde

Klute - 28-8-2009 at 20:47

Last year I prepared a bunch of salicylaldehyde from phenol, and now I looking for ideas of what to do with it..

One thing I started doing is salen complexes, reacting salicylaldehyde with ethylenedimaine, and complexing the dimine with a metal. Here is a nice protocole for Ni and Cu Salen complexes: Salen

I can also alkylate to 2-alkoxybenzaldehyde, and use that to form a phenylbutanone (already did it once).

Another interesting product could be substitued coumarins, by condensation with methyl acetoacetate or acetylacetone.

The Biginelli reaction, forming aryl tetrahydropyrimidines, looks nice too, aswell as the analoguous Hantzsch reacrion:Hantzsch

ANy more ideas, suggestions?

[Edited on 29-8-2009 by Klute]

jhullaert - 29-8-2009 at 01:51

The last one looks very nice indeed.

An idea of a less experienced chemist: Aldol condensation with aceton and then cyclisation. with one of the phenols not alkene methathesis.

DJF90 - 29-8-2009 at 06:36

Catechol can be made by oxidation with hydrogen peroxide. Benzofuran can me made by reacting the phenoxide with monochloroacetate, acidifying to extract the free acid and then cyclisation in Ac2O IIRC. Salcylaldehyde makes a nice complex with nickel itself. Digesting this in conc. ammonia for 20mins or so under reflux with an air condensor produced another complex. If necessary I can dig out the details for you.

entropy51 - 29-8-2009 at 06:50

A "bunch"? Sounds promising. Klute, if you haven't already, would you please post your synthesis of salicylaldehyde? TFSE didn't turn it up. I've never had good yields from this syn and would be interested in yours. Thanks!

DJF90 - 29-8-2009 at 07:30

Look in prepublication - "Mg mediated formylation of phenols"

panziandi - 29-8-2009 at 07:59

I tried a Reimer Tiemann reaction for forming salicylaldehyde I had attrocious yield, probably due to the fact I did not stir the recation, however the boiling should have mixed it and teh chloroform was added slowly. Another reason could have been that I left it to stand overnight before work up. Should give it another crack at some point. I do like the magnesium mediated formylation with paraformaldehyde, must do this at some point.

entropy51 - 29-8-2009 at 08:01

I've used Reimer-Tiemann as well. Yields are just lousy, no matter how you do them. I'll have to look at the Mg method.

Klute, as for uses of salicylaldehyde, I've methoxylated then reduced the CHO to CH2OH.

[Edited on 29-8-2009 by entropy51]

panziandi - 29-8-2009 at 08:38

There is a patent method for using the Reimer-Tiemann, using a gross excess of chloroform as the solvent and no/little water and addition of sodium hydroxide in portions, claims a yield higher than the original method. Also I was thinking of trying PTC in a parallel synthesis set up and comparing a few different methods.

DJF90 - 29-8-2009 at 08:39

I've seen a paper claiming 60% (IIRC) with a Reimer Tiemann on phenol - http://www.informaworld.com/smpp/content~db=all?content=10.1...

panziandi - 29-8-2009 at 08:41

Yes DJF90 I believe that is the method I was referring to

Here is a patent:

http://www.patentstorm.us/patents/4755613/fulltext.html

similar higher chloroform content and low water.

[Edited on 29-8-2009 by panziandi]

entropy51 - 29-8-2009 at 08:53

Thanks, guys! That is quite an interesting patent. :cool:

garage chemist - 29-8-2009 at 12:38

You can make coumarin from it by Perkin synthesis (reflux with acetic anhydride and freshly fused and powdered anhydrous sodium acetate). This is supposed to smell quite nice (never made it myself).
My attempt at the Perkin synthesis with benzaldehyde, which should have given cinnamic acid, was a failure though, so I never bothered trying it with the small amount of salicylaldehyde I have.

entropy51 - 29-8-2009 at 12:58

Quote: Originally posted by garage chemist

My attempt at the Perkin synthesis with benzaldehyde, which should have given cinnamic acid, was a failure though, so I never bothered trying it with the small amount of salicylaldehyde I have.

I feel much better knowing you had problems with the Perkin too. My yield was 12%. I think Vogel says 60%, which is hard to believe. I think it was Organikum who once said that all chemistry is a scam, or something like that. Sometimes I think he was right on the money.

Klute - 29-8-2009 at 16:16

Thanks for all the answers!

The Perkin looks like a good idea! I have enough Ac2O to try it out a few times, I will try with benzaldehde just to see how much I can get from it..

DJF90, I would love the details for the Ni complex of Sal, aswell as the NH3 digestion..

I never even bothered trying a Riemmer-tieman after reports of tarry product and low yields... Straight to gold with the Mg/HCHO! The reaction is simple but yet very interesting from a practical and theoritical point of view, very high yielding and uses easy to get chemicals.. Can't find any better!

I have roughly 150mL salicylaldehdye, counting a little commemrcial product too, that's what I call a bunch for a home made product, not realyy a liter or such

sorry if I disappoint you hehe

entropy51 - 29-8-2009 at 16:37

Quote: Originally posted by Klute

I have roughly 150mL salicylaldehdye, counting a little commemrcial product too, that's what I call a bunch for a home made product, not realyy a liter or such

sorry if I disappoint you hehe

Klute, that's no disappointment at all. The most I ever made in a run was about 10 mL.

Good job!

Paddywhacker - 29-8-2009 at 20:20

You could try mixed aldols with a variety of methyl ketones and then, maybe, hydrogenation of the resulting unsaturated ketone, as done in the raspberry ketone thread http://www.sciencemadness.org/talk/viewthread.php?tid=9706

The results are bound to be pleasant-smelling.

Klute - 30-8-2009 at 06:44

That's exactly what I meant by forming phenylbutanones! I have already made the 2-methoxyphenylbutanone, it does smell nice! I could always make it again as I only did a very small amount (<500mg)

I could try the 2-hydroxyphenyl couterpart, I don't think I've done it.. It must be simialr to the 4-hydroxyphenyl..

Paddywhacker - 30-8-2009 at 09:01

If the reaction works with acetone then it should also work with methyl ethyl ketone and methyl isobutyl ketone... both otc printing solvents.... maybe even acetaldehyde would work.

I wonder if a R-CH2-CO-R2 would form an aldol condensation just as readily.... things like cyclohexanone, menthone and camphor.

DJF90 - 30-8-2009 at 09:29

Cyclohexanone should work fine, Menthone should work ok under kinetic conditions, as the iPr group may cause steric problems for the thermodynamic enolate. Camphor may not work, but if it does the alkylation will occur at the 3-position (at least I think its the 3 position, start at the bridgehead and count round the largest ring, so that the carbonyl has the lowest possible position descriptor). The interesting thing about using MEK or MiBK instead of acetone is that there are two possible positions for alkylation...

Klute - 30-8-2009 at 10:08

Yes, I already used MEK, both with basic catlysis (linear product) and acid catalysis (branched product). Gaseous HCl seems like the best catalyst for the acidic condensation, although I've been wanting to try using Amberlyst-15 resin..

entropy51 - 30-8-2009 at 10:23

Quote: Originally posted by Paddywhacker

If the reaction works with acetone then it should also work with methyl ethyl ketone and methyl isobutyl ketone... both otc printing solvents.... maybe even acetaldehyde would work.

According to this reference benzaldehyde and acetaldehyde goes smoothly to cinnamaldehyde.

http://books.google.com/books?id=1B6ijcTkD5EC&pg=PA498&a...

DJF90, never mind. I can't work rxns in my head!

[Edited on 30-8-2009 by entropy51]

DJF90 - 30-8-2009 at 10:55

entropy that makes no sense, you mean MiBK?

Klute - 30-8-2009 at 17:49

I could also react it with a-chloroacetone to form a benzofuran ring:

http://www.ics-ir.org/jics/archive/v5/S1/article/pdf/JICS-5-...

I'm sure another base than KF/Al2O3 can be used with good results..

Using a chloroacetic ester and microwaves looks like a good idea too:

http://www.cyf-kr.edu.pl/~pcbogdal/benzofuran/

[Edited on 31-8-2009 by Klute]

densest - 30-8-2009 at 22:44

Isn't salicylaldehyde used to complex some ions like lanthanides and vanadium? Or is that salicylaldoximes? Or both?

DJF90 - 31-8-2009 at 08:44

Yes they're both used to complex some ions, like nickel, as I suggested above.

monoceros4 - 3-9-2009 at 00:48

Quote: Originally posted by densest

Isn't salicylaldehyde used to complex some ions like lanthanides and vanadium? Or is that salicylaldoximes? Or both?

According to Vogel the oxime is a good precipitant for several metals, yielding definite compounds that can be weighed directly. Copper is the analyte best suitable with salicylaldoxime but there are others.

Klute - 3-9-2009 at 01:02

Anymore info on salicyladoximes? Theses look interesting.. And easy to prepare...