Sciencemadness Discussion Board - Vanillin Extraction from OTC Vanilla extract.

Vanillin Extraction from OTC Vanilla extract.

Sedit - 10-6-2010 at 14:25

Like many experiments of mine I look around the house and think.... What can I play with. So having a look I got Vanilla which I decided I was going to extract just to find it being more of a pain in the ass then I initially assumed more then likely due to the shitty purity of the starting material. To get ya'll up to speed here is the short question thread discussion about this.

Quote:

Does anyone have the solublity data of the Vanillin Bisulfate adduct it either H2O or EtOH?

Im attempting to extract it from an impure OTC Vanilla extract which contains mostly H2O and some EtOH so I figured add sodium Metabisulfate till saturation and quickly filter then add EtOH to precipitate the adduct but I want to make sure I got what I desire.

UnintentionalChaos

Quote:

Buy a cheap "white" decorating vanilla. Boil down with something to help exclude air until the fumes aren't flammable, or watch until the temp hits 100C. I topped the beaker with tinfoil and a pinhole to help with this. Then chill the mixture, as vanillin has a pretty steep solubility curve. You should get white to off white (off white more likely) needles forming- let it cool undisturbed and slowly or you get mushy fine crystals that trap the solvent- molten vanillin may also oil out as it has a low melting point out but should freeze.

I have NMR verification that (at least as of 4 years ago) Wilton's clear decorator vanilla was all methyl vanillin with no ethyl vanillin or other flavors (at least of the product as isolated above and recrystallized from boiling water).

Department of Redundancy Department - Now with paperwork!

Sedit

Quote:

Thanks UC. I did a test tube run by adding "dirty" (ill explain in abit) Vanilla extract to Metabisulfate until no more would dissolve and filtered it. Upon adding more EtOH as expected the clear solution took a cloudy appreance and a fine white precipitate was noted but not isolated due to the small scale.

By Dirty I mean all kind of crap like glycols and sugers which I obviously don't want but its what I had on hand when i first decided to try it for the hell of it.

Im doing a small test as well along the lines of what you just stated and am evaporating the entire contents down to a syrup(more then likely) mainly to remove the EtOH and H2O then I was considering adding a .5:1:1 H2O/EtOH/Et2O mixture to dissolve the syrup and slowly allow to evaporate and see if any crystals form. If they indeed do I could adjust the ratios of the crystalizing solvents to get more bang for my buck. Indeed however I will search for the brand you made mention of because I want pure vanillin when im done just to say I did it.

PS: What about NH3 adduct, that should accomplish the same goal simular to how BnO is isolated forming the trimer and then a simple acid hydrolysis would recover my Vanillin correct. May be one of the simpler methods if proves true... No other way to find out Ill be right back , lol

Sedit

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Nope not even the slightest bit of precipitate using (aq) NH3 although the R-OH contents in the mix may possibly be solvating the adduct but I don't know. Ill get some cleaner material tommorow and give your metho a shot UC.

I must ask. Whats the need to exclude air from the mixture needed for? Am I doing this just to remove the EtOH and allow the Vanilin to precipitate due to its low solubility in H2O or is there something im missing?

Knowledge is useless to useless people.
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[hr]
Sedit

International Hazard

Nope not even the slightest bit of precipitate using (aq) NH3 although the R-OH contents in the mix may possibly be solvating the adduct but I don't know. Ill get some cleaner material tommorow and give your metho a shot UC.

I must ask. Whats the need to exclude air from the mixture needed for? Am I doing this just to remove the EtOH and allow the Vanilin to precipitate due to its low solubility in H2O or is there something im missing?

Heres what im working with and I have come to the conclusion that there is very little vanillin or ethylvanillin in over the counter tinctures.

In order,
H2O, Pure Vanilla extract, Alcohol, Sugar, Vanillin, Ethylvanillin, Benzodihydropyron and carmal color.

After slowly heating to evaporate the Alcohol there was two distinct precipitates the first layer being a dark oil like mass and the next layer being a baige powder that ends up mixing with the oil in the end.

Bisulfate adduct test only produced a small amount of beige powder that lightened up after washing with Et2O but treating with NaOH solution theres no real smell o Vanillin present, Iv always sucked generating any adduct so that don't tell me much.

I decanted to leave the bottom dark oil layer which I washed with with Chilled H2O and again decanted. Setting some aside I tryed to dissolve it in MEK... it didn't dissolve although the MEK took on some of the color. Evaporation of the MEK showed Needle crystals so thats possibly a good sign.

I added the dark oil and decided to try once again to form the ammonia adduct of the vanillin if that is indeed what is in the bottom oil layer and amazingly the bottom layer went into solution quickly becoming much darker then before. I wounder if the ammonia adduct is soluble in H2O and if so evaporation to remove excess NH3 and acid hydrolysis could lead to recovery even from a filthy starting material but time will tell.

Im more then likely going to go get better starting material to work with and will attempt to document that here for everyone with pictures of course as usuall.

Just thought I would share, Any thoughts on a better way?

Magpie - 10-6-2010 at 15:40

This is not a direct answer to your last question but I wonder if you could find some Mexican vanilla for a reasonable price. A friend gave me a pint of aqueous vanilla from Mexico and it made me wonder if this might be a better starting material.

[Edited on 10-6-2010 by Magpie]

not_important - 10-6-2010 at 16:10

Note that you used a boosted vanillia extract, and thus had all the conplexity of a natural product to deal with, plus the vanillin was just being used to stretch the natural product. If you must start with extract, try discount stores and look for the cheapest per volume stuff; check it to see that it has little to no vaniilia in it but only vanillin and/or ethyl vanillin.

Other places to try are professional baking or cooks supply stores, and Middle Eastern groceries or dry goods stores which sometimes have jars of vanillin.

You can get fairly pure vanillin powder online - search for "Krinos Vanillin Powder" or "Castella Vanillin Powde" for starters.

If starting with an extract, be it natural, artificial, or a mix, I'd consider adding sufficient NaHSO3 to be in several-fold excess of the aldehyde content - guess, excess bisulfite is what you want. Evaporate under low vacuum on a water bath to remove alcohol and most of the water. Extract with a little EtOAc, ether, toluene, or xylene, just to pull out any non-polar stuff. To the remaining solids add sufficient Na2CO3 to decompose the bisulfite addition product, add solvent ethanol or azeotrope isopropanol - you want some water at this point. Mix well, let sit for awhile with occasional stirring. Add an equal volume of acetone, filter, wash the solids with acetone. Evaporate the filtrate, recyrstalise by dissolving in boiling water, filtering, and cooling. This should give fairly pure vanillin and similar compounds.

Sedit - 10-6-2010 at 16:51

Thanks for the tip N_I. I was unaware that you can purchase pure vanillin anywhere over the counter so ill see what I can find.

The extraction you laid out is simular to what my initial thoughts where on performing the adduct. Issues appear when attempting to extract with Et2O after adding the bisulfate because an ugly emulsion forms. Im all out of xylene since I got a good cheep source of Ether and have been using that for quite a while now but I think that xylene would be better here in preventing an emulsion. Iv considered adding NaCl to aid in breaking the emulsion but I haven't gotten around to it yet.

I am in the middle of evaporating the NH3 "adduct" over the very low heat but just as the smell of NH3 lessens the smell of Vanilla gets stronger so I have a feeling that it decomposes with heat.

Im going to get better product but still toy with this dirty shit to make sure I know what im doing when I get down to the nitty gritty.

I Do have to say of all the interesting things iv seen I am quite shocked that the bottom oil layer did not dissolve in MEK. I have never seen many substances that didn't dissolve in MEK so it was quite a shocker when this layer just sat there.

not_important - 10-6-2010 at 17:24

The emulsion problem is why I suggested evaporating to near dryness, the sugar content and in some extracts propylene glycol or glycerol will give a syrup, although that may be somewhat crumbly if there's enough extra NaHSO3. So the extraction isn't your everyday sep funnel sort, but stirring in a beaker with the extraction solvent, the sugars will not disolve nor will the addition product, so they remain as a somewhat gooy mass.

Sugar syrups don't dissolve well in most alcohols and worse in less polar solvents, slowing adding acetone to a hot fairly concentrated solution of a sugar will sometimes precipitate it in a crystalline form while ordinary cooling or evaporative crystallsation fails.

Sedit - 11-6-2010 at 04:50

Iv concluded that if a solid ammonia adduct exist it can't be isolated from an (aq) solution because the heat appears to decompose it. I have some with a large amount of Bisulfate I am going to take down to dryness(goo basicly) and see how that goes.

Later today Im going to pick up two or three bottles maybe and have a go at it this weekend time permitting.

Sedit - 11-6-2010 at 13:53

I went out to the store today and decided that aside from buying pure Vanillin powder like N_I suggested you just are not going to find it at a reasonable price to make it worth it. Still I went and bought the cheepest 16oz bottle I could find being americas choice imitation vanilla.

Its ingrediants are nothing more then
H2O
Carmal color
Propyleneglycol,
Vanillin,
Ethylvanillin.

So an adduct should lend itself nicely here. Although some alterations will have to be made due to Propylene glycols high BP.

Anyone know how to find the percent of vanillin and ethylvanillin in this? Its funny I can bring up the ingrediants of the stuff I paint with or clean with, without a problem but finding out the contents of my food is some huge secret.

[Edited on 11-6-2010 by Sedit]

Sedit - 13-6-2010 at 13:13

Heres what I got so far and after tommorow don't know when im going to find time to work with this so bear with me.

Assumed amount of excess Sodium MetaBisulfite was added directly to the imitation vanilla until the smell all but dissapeared and was replaced by the smell of SO2.

This was slowly evaporated down as much as I could adding Dry IpOH on occassion because it was happening at an extremely slow rate assumingly due to Propylene glycol holding on to the water. After condensing it down to about 1/3 its volume crystals started to appea on the surface and it was allowed to cool precipitating a black almost crystaline mass. This was decanted and the mother liquor set aside for later.

A small sample was taken and added to Et2O but the Ether showed little effect at removing the source of discoloration. After trial and error with different solvents the best mixture was shown to be MEK which removes the color but has trouble breaking down the ass and a small amount of IpOH which seems to aid in breaking the mass but does little for the discoloration. When finished it leaves a fine off white precipitate behind assuming to be the adduct of the aldahyde content to be filtered and weighed which has not be done yet.

[edit]

Heres something that would be worth someones time if they where seriously involved in it and would work perfectly using the cheep over the counter product I mentioned.

Process for the extraction of vanillin

Assuming the CO2 is there to act as an inert gas I would assume N2 to work as well. It would be as simple as distilling the mixture to rid the vanillin into the sulfite collector then adding abit of H2SO4 till it dropped out of solution. No solvents no processing the adduct to clean it just pure and to the point vanillin extraction from a potentially large volume in relatively short order.

[Edited on 13-6-2010 by Sedit]

Sedit - 17-6-2010 at 19:28

I got a chance to return to the dryed product and I was sad to notice that the cleaning that appeared from the small scale test using MEK/IpOH was due to two factors I believe. One being precipitation of not completely dried crystals and precipitation of, something I discuss further, from the latent propylene glycol/water on the crystals.

So I decided to test this by adding the wash MEK/IpOH to the solute from the previous filtering and it did what was expected just not sure exactly what I have and why it precipitated this way.

On mixing there was an upper MEK/IpOH layer and a bottom brown Propylene glycol solution. At the interface of the two layers which precipitate was noticed and after leaving for a few days there was a material all over that had the appearence of tiny styrofoam beads. This is much more reminisent of past adduct runs the the first crop of crystals which where more hard and crunchy where this was more like tiny spheres forming a clumpy white mess.

So I think if I ever wanted to do this again(doubtful) I would run a few precipitation test on the condensed product. In due time I will complete the hydrolysis on each sample at different times to see which is my best bet at being the purest product.

[edit]
Being the eager chemist I am I couldn't help but try a small sample so a little was dissolved in a couple ML of H2O and H2SO4 dripped slowly in. Evolution of SO2 was noted and at one point this all but ceases and the solution becomes cloudy. On slight cooling of the heat formed from H2SO4 a small amount of oil was noted on top much greater with the second crop of precipitate then the first and I feel the first may just be mostly sulfites and sugars precipitating and the MEK/IpOH precipitated the clean(er) adduct. Pretty cool to watch an I cant help but wounder if concentration of the mother liquor is even needed. Perhaps either IpOH or MEK will precipitate the adduct without further process.

[Edited on 18-6-2010 by Sedit]

not_important - 17-6-2010 at 21:27

You do realize that MEK forms a bisulfite addition product too, although not as enthusiastically as aldehydes do? In some thread in the past I posted equilibrium values for several aldehyde and ketone bisulfite adducts where the bisulfite is not in excess.

right here http://www.sciencemadness.org/talk/viewthread.php?tid=7689&a...

MEK is roughly half as interested in forming adduct as are aldehydes.

[Edited on 18-6-2010 by not_important]

Sedit - 18-6-2010 at 04:54

DOH'

Yeh WTF am I thinking. I already am aware of this but abit of a brain fart I guess.

Damn...

Well thats going to screw up alot. I checked the test tube this morning after the SO2 smell subsided and there is indeed a vanillin smell in there but if MEK is present as well it might explain why I can't get the top layer to crystalize like I would expect from vanillin. Im going to try and free the adduct with a base but to be honest im about done with this experiment. I did notice a crystaline needle structure spread thruout the adduct could what im seeing be the two adducts being mixed with each other? One appears as needles while the other as small spheres more reminisent of adducts then the crystals.

Its mainly for academic curiosity and now with the added involvement of MEK with the vanillin its just not really worth my time or materials.

I think if I where to ever try this again I would attempt something more along the lines of patent 4898990 and try to simple distill the imitation vanilla into a Bisulfite solution or something along them lines.

Random - 23-8-2010 at 14:40

I have vanilla sugar that says on ingredient list:

vanilla
sugar

How to extract pure vanillin from that and is there a lot of it?

Sedit - 25-2-2011 at 12:10

I stopped by the health food store the other day and while there decided to look for pure Vanillin just to see if they had some. The place is a jumbled mess of tinctures, essential oils, Vitamines, Homopathic remedys, 35% H2O2, DMSO ect...ect..., you name it this place has it, they just don't have it organized so its a bitch to wade thru and I could very easy blow thru my wallet at this place since they got alot of cool stuff I like to play with. I got alot of fun stuff to play with one being cassia oil which I expected to smell like cinnamon. It don't, it smells like shit to me. I truely can't stand the smell of this stuff and I am woundering if I got the right thing since people mentioned turning this into Benzaldahyde. Funny to look around online and here how people love this Chinese cinnamon Cassia oil stuff yet when I as much as hold the bottle it takes hours for that disqusting smell to leave and I normally have to change my cloths. If this can be turned into Benzaldahyde I want to do it as soon as possible since I love BnO smell yet this Cassia is down right awful.

Anyway, back on topic, I did not find pure Vanillin but there was this and I thought I would take a shot since its only listed ingrediants is Vanilla extract and Maltodextrin.

The solubility of Maltodextrin appears to be almost Nil in EtOH while Vanillin is soluble. I can not seem to find a reference however for the exact solubility of Vanillin that I am comfortable with and seeing as im unsure exactly how concentrated this stuff is I decided to take the mythbusters approch to it that is "if its worth doing, its worth over doing".

I placed 70 grams of the powder into a funnel with a filter and proceeded to slowly add 200grams of EtOH thru it collecting an amber brown solution that needs a slight bit more filtering. Im placing this in the freezer right now to see if anything happens but I doubt much will change. Its mostly just a test and a storage spot until im able to distill off the EtOH and concentrate it more.

The point is pretty much mute now but for future reference I was woundering if I would have been better off with a different solvent such as DCM or Acetone. Ether could be a good option as well but I honestly have trouble working with it because the smell kind of makes me sick. It appears that Vanillin is soluble in a wide enough variety of solvents that seperation from the Maltodextrin should not be an issue however a spot evaporation test showed that im going to be left with more then likely a sticky mess of concentrated Vanilla extract that will need further purification.

Here is the MSDS for Vanillin.
Attachment: Vanillin msds.PDF (48kB)
This file has been downloaded 773 times

I was also woundering. Since Vanilla essential oils are nothing more then a solvent extract of the Vanilla bean this should be a pretty damn good source of Vanillin compaired to all this other shit on the market correct? Some sources seem to suggest up to about 29% Vanillin but I have no real idea what the other materials would be so purification might be hard. At the same time however what im more then likely going to be left with after this Alcohol evaporates is nothing more then the same exact thing only dirtier that one would get if they just bought a bottle of Vanilla essential oils.

Any thoughts or suggestions are greatly welcome, Im still not 100% sure how im going to turn the resulting goop I feel im going to get into pretty Vanillin crystals that I want. Its going to be a matter of some sort of wash and a recrystalization I just haven't decided on what sort of process to use.

Eclectic - 25-2-2011 at 17:47

You may be able to get to vanillin from a permanginate oxidation of Euginol (oil of clove, oil of cinnamon leaf).

Sedit - 25-2-2011 at 18:45

I have considered that a few times but have always came to the conclusion that before going thru that I would just as well order it. More often then not I just enjoy extracting and purifying substances that I have access to. Its obvious in the pattern I have here such as attempting to produce GAA from household stuff and things of that nature. I'v been doing this sort of thing since I was about 10 or 11 years old so I guess deep down inside its just part of the joy I get from chemistry.

I have a glimmer of hope in that as some small test samples have dried to show what may quite possibly be crystals of some sort. There is a slight iridescence when viewed thru back lighting and this is very reminisent of microcrystaline structures embedded in "crap" that has been observed over the years. I have decided to reduce the mother liquor until its either cloudy or a faint ring can be seen around the upper edge of the fluid line at which point it should be placed in the freezer and hopefully produce some sort of result in the form of precipitate or crystals to give me an idea of how to proceed from there. The temperature is being kept very low because I don't know the stability of vanillin all that well so it may be a while before I am able to continue with my quest.

Sedit - 2-3-2011 at 08:47

Something very confusing just happened and I would like some imput on this if possible. Normally my abilitys to clear up gunks from organic extracts is pretty good but this does not make much sense to me. I will have pictures and I took quite a few but I need to get a good paint program to resize them. Never get Advanced Paint, its one of the worst and most buggy photo editting programs I have ever delt with.

Heres what happened,

I evaporated the Alcohol extract down to its basics and filtered what I believe area latent Maltodextrin since they crystalized out rather quickly and remained stuck to the beaker with ease. These are clear crystals maybe a mm or less in size and I have not determined there structure just yet.

The remaining solution was condensed until it was a very viscous amber goop and a quick test showed acetone dissolves some of the material while leaving a taffy looking substance behind. Since Vanillin is soluble in Acetone to some extent it seemed a good way to proceed would be to re-dissolve the sludge in EtOH and attempt to crystalize on cooling from a 50/50 warm EtOH/Acetone mixture so that whatever the insoluble is would crash out of solution and further evaporation should yeild a more Vanillin enriched material. This is where something happened that I don't fully understand.

I added warm EtOH in order to make the mixture mobile and since this came from a EtOH extract one would expect all to dissolve yet there is now left behind an insoluble in warm EtOH that is a while powder estimated to be around .5-1 gram.

Any ideas what this could be? My only current suspicions are,
A: Remnant Maltodextrin which I think is unlikely given the stages is was filtered in and the appearence of what I believe is already Maltodextrin.
B: Oxidised material that is no longer soluble in EtOH, Possibly Vanillic acid. Yet this is suppose to be soluble in EtOH as well I believe.
C: I know jack shit about the other major materials present in the Vanilla bean and I just found one whos solubility in EtOH is odd.

Im left to just filter and proceed I guess but im working with small amounts of material and every transfer comes with loss. Im sure in the end the amount of Vanillin I would get out of this material is just to small for anything other then pictures.

[edit]

PS: All of this could have been avoided without a problem and possibly produced Vanillin crystals from the start if I had just extracted using warm Ether or something much more Non-polar the Alcohol.

[Edited on 2-3-2011 by Sedit]

Sedit - 3-3-2011 at 19:43

Im believe the remaining material that was left was something I really did not expect. I feel I may have overestimated the solubility of Vanillin in EtOH and Acetone. I washed that mystery powder in Acetone and it was pretty much pure white with little smell yet after sitting for about 1 hour I returned to find it smelled strongly of Vanilla(vapor pressure of crystals???)... I then dissolved it really easy with only a very small amount of water and this material was evaporated down to a glassy layer with a strong smell of vanilla.

However I can not seem to get it to crystalize. I see what might be something wanting to start but for the most part it just won't form crystals. I guess im going to wait till I get all of it before I attempt to crystalize it in a test tube using a mixture of 50:50 MeOH/DCM since I found an abstract stating that Chloroform and MeOH is the best mixture for growing the largest Vanillin crystals. MeOH forms needles and Chloroform made plates but combinded they formed large hybrides between the two. Im going to place a request soon enough for this whole paper to see what other material it contains.