| Pages:
1
2 |
Klute
International Hazard
Posts: 1378
Registered: 18-10-2006
Location: France
Member Is Offline
Mood: No Mood
|
|
Uses for salicylaldehyde
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]
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
|
|
|
jhullaert
Harmless
Posts: 13
Registered: 11-12-2008
Location: Ghent Belgium
Member Is Offline
Mood: No Mood
|
|
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
International Hazard
Posts: 2266
Registered: 15-12-2007
Location: At the bench
Member Is Offline
Mood: No Mood
|
|
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
Gone, but not forgotten
Posts: 1612
Registered: 30-5-2009
Member Is Offline
Mood: Fissile
|
|
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
International Hazard
Posts: 2266
Registered: 15-12-2007
Location: At the bench
Member Is Offline
Mood: No Mood
|
|
Look in prepublication - "Mg mediated formylation of phenols"
|
|
|
panziandi
Hazard to Others
Posts: 490
Registered: 3-10-2006
Location: UK
Member Is Offline
Mood: Bored
|
|
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
Gone, but not forgotten
Posts: 1612
Registered: 30-5-2009
Member Is Offline
Mood: Fissile
|
|
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
Hazard to Others
Posts: 490
Registered: 3-10-2006
Location: UK
Member Is Offline
Mood: Bored
|
|
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
International Hazard
Posts: 2266
Registered: 15-12-2007
Location: At the bench
Member Is Offline
Mood: No Mood
|
|
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
Hazard to Others
Posts: 490
Registered: 3-10-2006
Location: UK
Member Is Offline
Mood: Bored
|
|
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
Gone, but not forgotten
Posts: 1612
Registered: 30-5-2009
Member Is Offline
Mood: Fissile
|
|
Thanks, guys! That is quite an interesting patent.
|
|
|
garage chemist
chemical wizard
Posts: 1803
Registered: 16-8-2004
Location: Germany
Member Is Offline
Mood: No Mood
|
|
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
Gone, but not forgotten
Posts: 1612
Registered: 30-5-2009
Member Is Offline
Mood: Fissile
|
|
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
International Hazard
Posts: 1378
Registered: 18-10-2006
Location: France
Member Is Offline
Mood: No Mood
|
|
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
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
|
|
|
entropy51
Gone, but not forgotten
Posts: 1612
Registered: 30-5-2009
Member Is Offline
Mood: Fissile
|
|
| 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
Hazard to Others
Posts: 478
Registered: 28-2-2009
Member Is Offline
Mood: No Mood
|
|
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
International Hazard
Posts: 1378
Registered: 18-10-2006
Location: France
Member Is Offline
Mood: No Mood
|
|
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..
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
|
|
|
Paddywhacker
Hazard to Others
Posts: 478
Registered: 28-2-2009
Member Is Offline
Mood: No Mood
|
|
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
International Hazard
Posts: 2266
Registered: 15-12-2007
Location: At the bench
Member Is Offline
Mood: No Mood
|
|
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
International Hazard
Posts: 1378
Registered: 18-10-2006
Location: France
Member Is Offline
Mood: No Mood
|
|
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..
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
|
|
|
entropy51
Gone, but not forgotten
Posts: 1612
Registered: 30-5-2009
Member Is Offline
Mood: Fissile
|
|
| 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
International Hazard
Posts: 2266
Registered: 15-12-2007
Location: At the bench
Member Is Offline
Mood: No Mood
|
|
entropy that makes no sense, you mean MiBK?
|
|
|
Klute
International Hazard
Posts: 1378
Registered: 18-10-2006
Location: France
Member Is Offline
Mood: No Mood
|
|
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]
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
|
|
|
densest
Hazard to Others
Posts: 359
Registered: 1-10-2005
Location: in the lehr
Member Is Offline
Mood: slowly warming to strain point
|
|
Isn't salicylaldehyde used to complex some ions like lanthanides and vanadium? Or is that salicylaldoximes? Or both?
|
|
|
DJF90
International Hazard
Posts: 2266
Registered: 15-12-2007
Location: At the bench
Member Is Offline
Mood: No Mood
|
|
Yes they're both used to complex some ions, like nickel, as I suggested above.
|
|
|
| Pages:
1
2 |
![[*]](images/xpblue/default_icon.gif){kind=icon}
