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Author Topic: formation of N-N bond via oxidation  (Read 1087 times)

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kriggy

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formation of N-N bond via oxidation
« on: November 29, 2018, 09:56:14 AM »

Hey guys,
im brainstorming a bit about a way how to make a dimer via N-N formation via oxidation. I know hydrazine is made this way but is this method more videly aplicable? To be more specific, I would like to make a benzimidazole dimer that is joined via the N-N bond.

I think I could make it via step by step cyclization approach but since I have the benzimidazole in lab it seems the easiest method to try

Enthalpy

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Re: formation of N-N bond via oxidation
« Reply #1 on: November 30, 2018, 01:19:10 AM »

Hypochlorite to chloramines, then Wurtz?

Err, I fear I've put nonsense, but I just couldn't resist, sorry!
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kriggy

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Re: formation of N-N bond via oxidation
« Reply #2 on: November 30, 2018, 05:51:25 AM »

Haha thats what I was thinking but I cant find much info about those kind of reactions being applied on something else than ammonia -> hydrazine

AWK

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Re: formation of N-N bond via oxidation
« Reply #3 on: December 01, 2018, 06:06:10 AM »

Grignard compound from chloramine + chloramine with catalysis ?
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Enthalpy

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Re: formation of N-N bond via oxidation
« Reply #4 on: December 19, 2018, 11:30:15 AM »

And, are there already good news?

Anders Hoveland made many syntheses with unsaturated azo rings before entering the university, but he hasn't been active here for a while. Maybe you can find him on the Web, he had a website.
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TheUnassuming

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Re: formation of N-N bond via oxidation
« Reply #5 on: December 20, 2018, 07:42:02 AM »

Apologies, been a while since I've dropped by so missed this thread when it was active. 

If you are still working on this, you might check out work by Stahl (DOI: 10.1021/jacs.8b05245)  and Baran (DOI: 10.1021/ja5013323) labs in this area.  If it will work with benzimidazoles though... who knows.
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When in doubt, avoid the Stille coupling.

kriggy

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Re: formation of N-N bond via oxidation
« Reply #6 on: December 21, 2018, 12:05:36 AM »

Thanks for the papers, both are quite interesting. Im no longer on this though Im on one project now and we will be starting another one soon I think and this was just an random idea. I looked into the literature a bit and found some papers about the N-N linked benzimidazoles and they (and the intermediates) are bit unstable.

The Stahl procedure looks like something I could try just for fun to see if it works if I can find the correct Cu source.

Enthalpy

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Re: formation of N-N bond via oxidation
« Reply #7 on: December 21, 2018, 01:57:21 AM »

In Stahl (DOI: 10.1021/jacs.8b05245) (I access only the abstract) I don't grasp where the hydrogen shall come from to split the N-N bond

c1ccccc1Nc2ccccc2  ::equil::  c1ccccc1N(c2ccccc2)N(c3ccccc3)c4ccccc4 ??

The 1atm O2 supposedly serves to consume the hydrogen atoms weakly bonded to N and provoke the N-N bonding.

Once this hydrogen is bonded to oxygen, I imagine it is irreversibly unavailable.

Do I misunderstand something?

Or could it possibly be instead that the still unbonded carbazole displaces a diphenylamine from the N-N compound, gives it a hydrogen and creates the cross-coupled N-N compound? At least the curve of species concentration versus time supports this scenario.
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