[sharbeldam]

Even when we break the aromaticity of the amine (like pyrolle) once we protonate it?

[rolnor]

Maybe 2,4,6-trinitroaniline is less basic then acetamide? And more acidic even if non-protonated?

[sharbeldam]

Thats a great example rolnor, I guess because of the strongly electron withdrawing groups?
What about the amidic nitrogen vs pyrollic nitrogen in LSD? if pyrolle gained an electron we lose aromaticity which much decreases the basicity of the pyrolle, shouldnt that make it less basic than amide? or the carbonyl effect is stronger?

[sharbeldam]

I just decided to attach a pic to make it more clear, I understood  that N3 is less basic than N1, inspite of the fact that N1 will lose its aromaticity once it gets protonated which i hear is very bad?

[hollytara]

You can change the basicity in a number of ways....

tris (tirfluoromethyl) amine is essentially nonbasic - does not form salts with acids. 

https://science-of-synthesis.thieme.com/app/text/?id=SD-018-01386

As far as amides vs pyrrole.  Protonated pyrrole has a pKa of 0.4, while protonated amides have pKa values less than zero: but protonation of amides most often occurs on the O not the N!

[sharbeldam]

Thanks holly
just for the record, the literature gives different pka values of pyrolle conjugate acid, some give negative values, hence where the confusion come from, but i do think it's 0.4 as well and hence it is indeed more basic than the nitrogen of amides.

[hollytara]

Since the amides tend to protonate on O rather than N, I am sure the pyrrole is more basic than the amide N.  Is it more basic than the amide O?  Close enough that other factors may tip it one way or the other.