ergoamide
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Selective reduction of N-alkyl-dinitroanilines to N-alkyl-nitrophenylenediamine
Specifically this is regarding the synthesis of 2-(diethylaminoethylamino)-5-nitroaniline otherwise known as
N1-(diethylaminoethyl)-5-nitro-1,2-phenylenediamine.
p-nitro-o-phenylenediamine is commercially available and reasonably cheap to. The problem comes when benzimidazoles are then N-alkylated that you end
up with a mixture of the 5 and 6 isomers when only the 5 isomer is desired. The easiest way to this is through the above mentioned n-alkylated
nitrophenylenediamine. This however is not commercially available and as far as I know p-nitro-o-phenylenediamine cannot be selectively alkylated.
Thus the solution to my problem would seem to be to get the 2,4-dinitroaniline, alkylate that then selectively reduce to the phenylenediamine. This
reduction can be accomplished by bubbling H2S through a concentrated ammonia solution.
A link for this procedure is here
Selective dinitroaniline reduction
It is on Page 660 just incase it oesn't go straight to the right page, loads of cool reactions there though are can be helpful.
Anyway there is no way I want to work with H2S so it would appear that reduction is a no go except that in a google search another book mentions the
same comound being produced by reduction with ammonium sulfide. Naturally I assume thats what's going on with the H2S reduction aswell just it's being
made in-situ. The only problem is I can't find a single other mention of it on google.
If someone has some more information on this topic it would be greatly appreciated or if someone has an alternative procedure that would work aswell
or better, I saw a mention of sodium sulfide somewhere a while ago aswell.
My real question in the end is will it work with N-alkylated derivatives. I can't see any reason why it wouldn't work with a N-alkylated derivtive but
I could be wrong due to steric hindrance maybe although I doubt it.
Any information much appreciated
Ergo
[Edited on 3-3-2009 by ergoamide]
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not_important
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This is the Zinin reduction, tons of references out there.
https://sciencemadness.org/talk/viewthread.php?action=attach...
https://sciencemadness.org/talk/viewthread.php?tid=3681&...
http://dspace.nitrkl.ac.in:8080/dspace/bitstream/2080/465/1/...
...
[Edited on 3-3-2009 by not_important]
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ergoamide
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Thanks not-important, the search engine here wasn't workin for me last night. No matter what I typed in it came up with no results. The thread on
3-nitroaniline perchlorate (i think that what the title was) I found on a google search a few days ago and found it reasonably useful and there were a
couple other threads on here that helped but most dealt with total reduction or unselective partial reduction. But thanks for the help I got some
reading to do
Ergo
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