Sciencemadness Discussion Board

D-tartaric acid

new-b - 4-8-2007 at 15:20

Hi everybody,

I've red somewhere I don't remember that it's possible to get a racemic solution of d-tartaric acid and l-tartaric acid from l-tartaric acid in hot aqueous KOH solution. (Probably by the formation of the "enolate"and a subsequent protonation of the enolate on both side...)

My question is what do you think would be the best way to isolate these enantiomers?Chromatography (silica, what solvent)? Cristallization? Is there a enantiomeric molecule who can only cristallize the D-tartaric acid?

Eclectic - 4-8-2007 at 15:32

You can try to grow very large crystals and the separate them visually. AIR, you get mirror image crystals of pure isomers.

Nerro - 4-8-2007 at 15:52

Is it feasable to try to grow large single crystals from a racemic mixture? (large = >1 cm)

Eclectic - 4-8-2007 at 16:16

I seem to recall that tartaric acid was one of the first compounds separated into optically pure isomers, with the aid of a magnifying glass and a pair of tweezers. :o

Oh yeah, some obscure old fart named Louis Pasteur, in 1847.


[Edited on 8-4-2007 by Eclectic]

new-b - 4-8-2007 at 19:38

From what i read :
The tartaric acid sodium-ammonium salt is unusual among racemic mixtures in that during crystallization it can separate out into two kinds of crystals, each composed of one isomer, and whose macroscopic shapes are mirror images of each other. Louis Pasteur was thus able to separate the two enantiomers by picking apart the crystals.

So now how to you do a sodium-ammonium salt. Never heard of a mixed salt?????

Nicodem - 4-8-2007 at 23:27

Indeed it was a stroke of luck that Pasteur choose a compound that forms aglomerates instead of racemic compound crystals. Less than 10% enantiomeric compounds have this property.
Quote:
Originally posted by new-b
So now how to you do a sodium-ammonium salt. Never heard of a mixed salt?????

I would assume it is as easy as to neutralize tartaric acid with 1/2 eq. NaOH and 1/2 eq. NH3 and crystalize the double salt.

Eclectic - 4-8-2007 at 23:39

The sodium-potassium salt (Rochelle salt) will easily grow large crystals...

Sauron - 5-8-2007 at 02:44

Chromatography would be no help unless you are going to apply chiral chromatography on a prep scale in which case you are pretty much on the cutting edge.

The serendipitous physical seperation of tartaric acid's enantiomers manually notwithstanding, the usual more general methid is to make a salt of the racemic tartaric acid with an optically pure base (often an alkaloid) and then you can seperate the two salts by conventional physico-chemical methods.

Naturally occuring tartaric acid is optically pure. The unnatural enantiomer is available commercially but a lot more expensive.

By the way D and L do not mean the same thing as d and l. One refers to the absolute configuration and the other to the optical rotation (+) or minus (-) as determined on a polarimeter. The polarimeter is of course the only way to tell just how optically pure something is (we talk in terms of ee (enantiomeric excess) and the reading on such an instrument depends on solvent, temperature, concentration, and length of optical path in sample tube. Great fun! especially with a plain jane optical model rather than a fancy schmancy digital instrument with a LED or LCD display.

new-b - 5-8-2007 at 08:13

Any interesting ideas about an OTC optically pure base who could serve the purpose of separating the D-tartaric acid from the L-tartaric acid?

Or, do you think D-tartaric acid is a watched substance and suspicious to order for any reasons?
What do you think about sciencelab.com they say they sell to individuals :

http://www.sciencelab.com/page/S/PVAR/SLT3046

Eclectic - 5-8-2007 at 08:37

Order from a brewing and winemaking supply. MUCH cheaper.

pantone159 - 5-8-2007 at 09:24

I think that Pasteur was additionally lucky, in that his compound only formed the chiral crystals at specific temperatures, which just happened to match those on his windowsill (or whatever).

I've never used ScienceLab.com, but I have heard multiple bad things about them. There is a thread about them on this board somewhere.

new-b - 5-8-2007 at 09:24

Quote:
Originally posted by Eclectic
Order from a brewing and winemaking supply. MUCH cheaper.


I wanna get the pure D-tartaric acid not the L.

Eclectic - 5-8-2007 at 09:47

I thought you might want to try making it from the racemate.

The sodium ammonium salt crystallized below 28 C seems the only useful one for physical separation. If you get good seed crystals of each enantomer, you should be able to get good separation by slow evaporation of a racemic solution using one seed of each.

There are also organisms that consume the natural form of the ammonium salt, and leave the other in the ferment.

new-b - 5-8-2007 at 12:06

What if you use only one seed crystal of the D form???You'll get one big crystal of the D form plus lots of small crystals of the L form. Am I right?

new-b - 5-8-2007 at 16:00

Quote:
Originally posted by Eclectic
I thought you might want to try making it from the racemate.

The sodium ammonium salt crystallized below 28 C seems the only useful one for physical separation. If you get good seed crystals of each enantomer, you should be able to get good separation by slow evaporation of a racemic solution using one seed of each.

There are also organisms that consume the natural form of the ammonium salt, and leave the other in the ferment.


Do you know the name of these organisms?

Sauron - 5-8-2007 at 16:22

And why do you want D-tartaric acid, exactly?

And why are you worried about whether or not it is watched?

I mean, just because it is specifically mentioned in the literature as being the resolving agent of choice for various optically active organic bases that just happen to be optically active?

What a coincidence!

new-b - 5-8-2007 at 17:00

it's the best way to isolate optical molecule. That's it

Eclectic - 5-8-2007 at 18:04

Google "Pasteur tartaric-acid isomers separation"


If you don't seed with a good crystal of each enantomer, you won't
have any control over where crystallization of the unseeded enantomer starts crystallizing. Ideally, you want one large crystal of each with good physical separation

Sauron - 5-8-2007 at 22:30

It's ONE way to resolve SOME optical isomers.

It is not the be all and end all of such resolutions.

The pharm industry is being forced to go to chiral chromatography so that field is making leaps and bounds.

There are also enzymatic methods - certain enzymes, for example papain, will hydrolyze the anilide os some amino acids selectively, leaving the free L-acid while not touching the D-form anilide, the two are then easily seperable.

Not all optically active compounds are bases, and thus, the tartaric acid enantiomers are not useful for them. The alkaloids are by definition nitrogenous bases. By sheer coincidence the amphetamines are too.

So what are you wanting to resolve?

Optical resolution by crystallization, is laborious and tedious. But, hey, knock yourself out.

ergoamide - 6-8-2007 at 04:05

Alkaoids are more than just nitrogenous bases though, amphetmine is NOT one. To be an alkaloid it must be found naturally, i.e in plants generally although most animals have them but much lower concentrations.

Oh and your local supermarket will have what you are after. Also learn what chemicals are watxhed and what is not. I mean asking if THIS is watched screams lack of knowledge and is a very obvious clue your doing something your not supposed to be.

[Edited on 6-8-2007 by ergoamide]

Sauron - 6-8-2007 at 06:51

I am well aware of what an alkaloid is and isn't. But thanks.

The local supermarket certainly does not have D-tartaric acid, all they will have is the L-isomer, the natural one.

new-b - 6-8-2007 at 07:28

Quote:

I mean asking if THIS is watched screams lack of knowledge and is a very obvious clue your doing something your not supposed to be.

[Edited on 6-8-2007 by ergoamide]


The fact that I'm asking if it's a watched substance doesn't mean by itself that I'm obviously doing something wrong. I was just asking about it because I don't want to get hasstle by ordering a watched substance.

solo - 27-4-2008 at 16:28

Quote:
Originally posted by Sauron
I am well aware of what an alkaloid is and isn't. But thanks.

The local supermarket certainly does not have D-tartaric acid, all they will have is the L-isomer, the natural one.



.........needless to say he naturally occurring form of the acid is L-(+)-tartaric acid or dextrotartaric acid. Note, that the dextro and levo prefixes are not related to the D/L configuration (which is derived from the reference D- or L-glyceraldehyde), but to the orientation of the optical rotation, (+) = dextrorotatory, (−;) = levorotatory...........source,

http://en.wikipedia.org/wiki/Tartaric_acid

While on on the subject there is a patent I'm looking for that resolves the l-isomer to d,l.....using Palladium.......solo


[Edited on 27-4-2008 by solo]