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Chemistry Forums for Students => Organic Chemistry Forum => Organic Chemistry Forum for Graduate Students and Professionals => Topic started by: joc on April 26, 2010, 04:59:46 AM

Title: Which N atoms in caffeine is the least basic
Post by: joc on April 26, 2010, 04:59:46 AM
Please help.

Pls refer to the attached file for the structure of caffeine.

The question is which N atom in caffeine is the least basic.

I think the Ngamma is the least basic because the electron pair is involved in an aromatic ring system (Huckel's rule).  However, some suggest that it is the Nbeta is the least basic because the lone pair is delocalized to the two neighbouring strongly electron withdrawing C=O groups.  Which one is more likely to be true?

Thanks a million!

joc
Title: Re: Which N atoms in caffeine is the least basic
Post by: Doc Oc on April 26, 2010, 08:17:59 AM
I would also wager on beta, but I'm not an expert with nucleotide chemistry.
Title: Re: Which N atoms in caffeine is the least basic
Post by: Schrödinger on April 26, 2010, 08:21:08 AM
Something tells me it is Nbeta.

When you try to draw some of its resonance structures, you can come up with the following(see figure attached) :

In addition to the stabilization due to aromaticity in the figure, the beta N is attached to 2 C=O groups.

I'm definitely not sure, but I thought I'd give it a shot


Oh...and one more thing. How do I attach a figure without having to attach a file?
I mean can I copy a picture from Chemdraw and just paste it here?

Title: Re: Which N atoms in caffeine is the least basic
Post by: nj_bartel on April 26, 2010, 01:01:20 PM
My guess would be beta too.
Title: Re: Which N atoms in caffeine is the least basic
Post by: joc on April 26, 2010, 09:58:24 PM
Thanks for your input. 

By the way, is there any source on the internet on the data of pKb values or pKa values of the common natural organic compounds such as caffeine.  What I mean is for all the N atoms or OH groups.  I have tried to search but can only get the values for the most basic one or the most acidic one.

Thanks again.
Title: Re: Which N atoms in caffeine is the least basic
Post by: MissPhosgene on April 26, 2010, 10:03:05 PM
Hello,

   I doubt you will find tables for that specifically. However, you could look at  pka tables and try to deduce..

I have to use this one in class and it's really really good...

http://evans.harvard.edu/pdf/evans_pKa_table.pdf

Title: Re: Which N atoms in caffeine is the least basic
Post by: demoninatutu on June 18, 2010, 01:52:09 AM
This one turns out to be a little trickier than I expected. I'm going with the gamma nitrogen for the same reason you suggested, it's aromatic. Aromaticity trumps conjugation.
Title: Re: Which N atoms in caffeine is the least basic
Post by: toddwick on August 05, 2010, 12:09:22 PM
I would say that depending on the aromatic nature of the entire molecule, which I'm sure has been explored (didn't do a literature search myself so that may not be true), both beta and gamma could be argued as the least basic.  I would suggest trying to find some sort of modeling program and seeing what happens.  I'm not exactly sure how one would come up with an approximation on the lone pairs relative basicities, but I am positive that you could find some protocol that could give you at least a qualitative (which is stronger) judgment.

If you have access to Gaussian thats a great start.