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Chemistry Forums for Students => Organic Chemistry Forum => Organic Spectroscopy => Topic started by: CHEKAL on January 06, 2013, 04:13:07 PM

Title: NMR diastereomers
Post by: CHEKAL on January 06, 2013, 04:13:07 PM
how would i be able to distinguish between cis and trans diastereomers using H-NMR? i know its something to do with the coupling constant.

also, how would i be able to determine a rough ratio of cis:trans diasteroisomers using H-NMR?

thanks
Title: Re: NMR diastereomers
Post by: discodermolide on January 06, 2013, 04:15:59 PM
What are cis and trans diastereoisomers? What exactly are you referring to here?
Title: Re: NMR diastereomers
Post by: CHEKAL on January 06, 2013, 04:25:28 PM
i have a compound with two chiral centres, cis being both centres have the same configuration relative to one another, trans being different configuration to one another
Title: Re: NMR diastereomers
Post by: discodermolide on January 06, 2013, 04:31:36 PM
i have a compound with two chiral centres, cis being both centres have the same configuration relative to one another, trans being different configuration to one another

You mean like this, for example?
Title: Re: NMR diastereomers
Post by: CHEKAL on January 06, 2013, 04:33:22 PM
yes, ive run the nmr spectrum of the compound, i just need to distinguish between them and determine an approximate ratio of the two relative configurations
Title: Re: NMR diastereomers
Post by: discodermolide on January 06, 2013, 04:40:02 PM
Well you can look at the ratio of the peaks next to the chiral centers.
The coupling constants for the H-H coupling should be different, look up the Karplus equation.
This of course if you can differentiate the peaks.
Title: Re: NMR diastereomers
Post by: CHEKAL on January 06, 2013, 04:46:25 PM
which configuration would have a higher coupling constant?
Title: Re: NMR diastereomers
Post by: discodermolide on January 06, 2013, 04:50:12 PM
Probably the anti configuration. As I suggested look up the Karplus equation.
This tells you the relationship between the J value and the angle between the two protons.
Title: Re: NMR diastereomers
Post by: CHEKAL on January 06, 2013, 05:01:22 PM
how would i do it in the case of no peak of the adjacent carbons to the chiral centres? i have an aziridine and the predicted spectrum nor my actual spectrum does not show any singlets that havnt been accounted for
Title: Re: NMR diastereomers
Post by: discodermolide on January 06, 2013, 05:04:35 PM
You mean you have a cis and trans aziridine? Like this?

Title: Re: NMR diastereomers
Post by: CHEKAL on January 06, 2013, 05:07:29 PM
yes, i will get a structure uploaded, watch this space
Title: Re: NMR diastereomers
Post by: CHEKAL on January 06, 2013, 05:15:19 PM
structures
Title: Re: NMR diastereomers
Post by: discodermolide on January 06, 2013, 05:20:55 PM
I would expect that the trans coupling would be larger than the cis coupling.
You should easily see this in the NMR.
Title: Re: NMR diastereomers
Post by: CHEKAL on January 06, 2013, 05:30:31 PM
how would i be able to see this?
Title: Re: NMR diastereomers
Post by: discodermolide on January 06, 2013, 05:32:11 PM
The chemical shifts of the protons should be quite different, each will be a doublet the distance between the lines is the coupling constant, J in Hz.
Title: Re: NMR diastereomers
Post by: CHEKAL on January 06, 2013, 05:36:41 PM
most lines are doublets yes, does that mean a triplet would have 6 peaks too?
Title: Re: NMR diastereomers
Post by: discodermolide on January 06, 2013, 05:38:28 PM
A triplet has three peaks, in a 1:2:1 ratio.
Title: Re: NMR diastereomers
Post by: CHEKAL on January 06, 2013, 05:40:11 PM
then which peaks would appear as doublets due to coupling between the different configurations?
Title: Re: NMR diastereomers
Post by: discodermolide on January 06, 2013, 05:44:24 PM
Each of the protons on the aziridine ring will appear as a doublet, integrating for 1H.
Title: Re: NMR diastereomers
Post by: CHEKAL on January 06, 2013, 05:49:50 PM
oh i see! thanks :) does this mean the difference in hight between the two peaks would give an approximate ratio of the two configurations in the yield?
Title: Re: NMR diastereomers
Post by: discodermolide on January 06, 2013, 05:51:12 PM
Yes that is correct. If you measure the integrals you can estimate the proportions of each diastereoisomer.