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Chemistry Forums for Students => Organic Chemistry Forum => Topic started by: goldy on August 24, 2010, 07:51:23 AM

Title: Problem in compound identification
Post by: goldy on August 24, 2010, 07:51:23 AM
Hello everybody
I have seperated one compound fron the medicinal plant. This compound seems single spot on TLC (both Np and RP column). But in HPLC using MeOH and water(with 0.1%TFA) it shows 4 peaks. When I injected in LC/MS it shows the same four peaks with same molecular mass. Can anybody guess what kind of compounds have this kind of property?
Any kind of suggestion will be appriciated.
thank you so much.
Title: Re: Problem in compound identification
Post by: research on August 24, 2010, 10:15:19 AM
Hello everybody
 But in HPLC using MeOH and water(with 0.1%TFA) it shows 4 peaks. When I injected in LC/MS it shows the same four peaks with same molecular mass. Can anybody guess what kind of compounds have this kind of property?
in regard the same molecular mass that you have mentioned, I guess they must be isomer
Title: Re: Problem in compound identification
Post by: Mesogen on August 24, 2010, 11:06:41 AM
Hi Goldy,

A few questions...

What solvent systems are you running the TLCs in? How well separated are the peaks in the LC/MS? What are the fragmentation patterns like in the MS?

Title: Re: Problem in compound identification
Post by: cundi on August 24, 2010, 11:23:27 AM
I agree with Research. They must be isomers.
The only thing is to known if you had isolated only one isomer or four. Sometime, compuonds can suffer epimerization of their quiral centers.
Inject several times the same sample in HPLC. (for example time 0, 1h 2h, 12h, 24h,... 5 days) and check if the ration  between 4 peaks is always the same. If not, it means that your compound/s are not stable in this analysis conditions.
Title: Re: Problem in compound identification
Post by: discodermolide on August 24, 2010, 12:36:56 PM
If you are getting a separation, collect the eluates from the LC , evaporate them to dryness and run nmr experiments to identify the compounds. You only neey 100-200 micro-grams to do this.
Title: Re: Problem in compound identification
Post by: lavoisier on August 24, 2010, 01:24:09 PM
Hello everybody
I have seperated one compound fron the medicinal plant. This compound seems single spot on TLC (both Np and RP column). But in HPLC using MeOH and water(with 0.1%TFA) it shows 4 peaks. When I injected in LC/MS it shows the same four peaks with same molecular mass. Can anybody guess what kind of compounds have this kind of property?
Any kind of suggestion will be appriciated.
thank you so much.
Hi goldy,
I think first of all you need to understand if the single spot you isolated by LC is indeed one single substance or not. You could simply run an NMR. I assume you have at least a vague idea of what the structure might look like.
If it is one substance, then one must conclude the HPLC/LCMS conditions cause degradation.
If it isn't, then no surprise, HPLC/LCMS is often more resolved than TLC, and you already have multiple compounds to start with.
Concerning the fact that they might be isomers, be careful not to over-read the LCMS. Sometimes one mass streaks all along the chromatogram. If indeed they do have the same mass, the first thing that springs to my mind is terpene-like substances, you know, full of double bonds that are easy to isomerize, hydrate, etc....
Title: Re: Problem in compound identification
Post by: goldy on August 25, 2010, 04:00:28 AM
Thank you everyboy for your kind suggestion. I will run the NMR of this compound. In case they are the isomers then should I have to collecet the all four peaks because it gets seperated into 4 peak or I can analyse them in the present condition?
I hope for your suggestion.
Title: Re: Problem in compound identification
Post by: AC Prabakar on September 04, 2010, 07:11:31 AM
Hello everybody
I have separated one compound fron the medicinal plant. This compound seems single spot on TLC (both Np and RP column). But in HPLC using MeOH and water(with 0.1%TFA) it shows 4 peaks. When I injected in LC/MS it shows the same four peaks with same molecular mass. Can anybody guess what kind of compounds have this kind of property?
Any kind of suggestion will be appriciated.
thank you so much.
Hi goldy,
I think first of all you need to understand if the single spot you isolated by LC is indeed one single substance or not. You could simply run an NMR. I assume you have at least a vague idea of what the structure might look like.
If it is one substance, then one must conclude the HPLC/LCMS conditions cause degradation.
If it isn't, then no surprise, HPLC/LCMS is often more resolved than TLC, and you already have multiple compounds to start with.
Concerning the fact that they might be isomers, be careful not to over-read the LCMS. Sometimes one mass streaks all along the chromatogram. If indeed they do have the same mass, the first thing that springs to my mind is terpene-like substances, you know, full of double bonds that are easy to isomerize, hydrate, etc....



Yes.First check simple NMR(1H and C-13).This will give idea about your expected compound and compound purity.
IR spectrum also can give clarity regarding compound purity.
Title: Re: Problem in compound identification
Post by: research on September 05, 2010, 11:01:48 AM
is it possible to assume that they are enantiomer two by two? I mean is it possible for a plant to make a pair of enantiomer?  :o
if this happens so you need a chiral reagent or chiral environment as whole to separate them.
Title: Re: Problem in compound identification
Post by: discodermolide on September 05, 2010, 11:59:59 AM
is it possible to assume that they are enantiomer two by two? I mean is it possible for a plant to make a pair of enantiomer?  :o
if this happens so you need a chiral reagent or chiral environment as whole to separate them.

Never heard of a plant making a racemate!
Title: Re: Problem in compound identification
Post by: goldy on September 06, 2010, 03:55:14 AM
is it possible to assume that they are enantiomer two by two? I mean is it possible for a plant to make a pair of enantiomer?  :o
if this happens so you need a chiral reagent or chiral environment as whole to separate them.

Never heard of a plant making a racemate!
http://www.springerlink.com/content/h475134g534qw462/fulltext.pdf
Title: Re: Problem in compound identification
Post by: goldy on September 06, 2010, 03:58:14 AM
is it possible to assume that they are enantiomer two by two? I mean is it possible for a plant to make a pair of enantiomer?  :o
if this happens so you need a chiral reagent or chiral environment as whole to separate them.
http://www.springerlink.com/content/734677147649442u/fulltext.pdf
Title: Re: Problem in compound identification
Post by: discodermolide on September 06, 2010, 05:32:08 AM
is it possible to assume that they are enantiomer two by two? I mean is it possible for a plant to make a pair of enantiomer?  :o
if this happens so you need a chiral reagent or chiral environment as whole to separate them.
http://www.springerlink.com/content/734677147649442u/fulltext.pdf

Racemised during isolation
Title: Re: Problem in compound identification
Post by: demoninatutu on September 06, 2010, 09:47:34 PM
Quote
Racemised during isolation

To explain discodermolide's answer a little more fully, it's not the plant that's making a racemic mixture, the racemisation occurs afterwards in the methanol mixture at elevated temperatures. This means that you could be having the same problem yourself, especially as you're running your HPLC in MeOH.

And in reply to your earlier question, you will have to analyse all four peaks separately. I also recommend a mass spectrum for each compound.
Title: Re: Problem in compound identification
Post by: discodermolide on September 07, 2010, 12:45:33 AM
is it possible to assume that they are enantiomer two by two? I mean is it possible for a plant to make a pair of enantiomer?  :o
if this happens so you need a chiral reagent or chiral environment as whole to separate them.
http://www.springerlink.com/content/734677147649442u/fulltext.pdf

Why should Nature make racemates? This would be a most inefficient way to produce the substances the plant or animal requires unless the two enantiomers have completely different activity which is likely but of no use to the biological system, especially when the compounds are used for predator defense etc.
Over millions of years it has had time to develop effective enantioselective synthesis even of the most complex chemical structures, Homo Sapiens make racemates in their laboratories.
Title: Re: Problem in compound identification
Post by: goldy on September 07, 2010, 01:49:34 AM
Quote
Racemised during isolation

To explain discodermolide's answer a little more fully, it's not the plant that's making a racemic mixture, the racemisation occurs afterwards in the methanol mixture at elevated temperatures. This means that you could be having the same problem yourself, especially as you're running your HPLC in MeOH.

And in reply to your earlier question, you will have to analyse all four peaks separately. I also recommend a mass spectrum for each compound.
I am running HPLC in ambient temperature. These compounds are overlapping with each other. I also injected them in mass and all four peaks have same mass (lil difference in dicimal value). I want to separate these compounds but doesn't seem possible.
Title: Re: Problem in compound identification
Post by: lavoisier on September 07, 2010, 01:38:08 PM
Unless you're using chiral HPLC, you won't see two enantiomers as two separate peaks.
So 4 peaks, on a non-chiral HPLC column, which have all the same mass (this should be checked by MS-search), are 4 isomers.
This doesn't imply they are stereoisomers (they could be constitutional isomers), and doesn't answer your initial question.

The NMR of your original isolated spot is what you need first of all.

You could also run the LCMS in basic conditions.