Sciencemadness Discussion Board

N-(1-Naphthyl)ethylenediamine

Waffles SS - 23-12-2013 at 08:11

Quote:




This compound can be prepared by the reaction of 1-naphthylamine with 2-chloroethanamine

Wiki


I dont think this is possible to make N-(1-Naphthyl)ethylenediamine from 1-naphthylamine with 2-chloroethanamine.I think self condensation of 2-chloroethanamine free base will happen.

Someone has better idea or method for making it?


[Edited on 23-12-2013 by Waffles SS]

Dr.Bob - 23-12-2013 at 08:28

The simplest way to make that would be a Buchwald RXN on 1-naphthylbromide with either 1,2-diaminoethane, or better, the mono-protected version. BocEDA is ideal for that. That would be ideal.

Alternatively, if you have the amine already, I would do a reductive amination with Boc-Gly-aldehyde, that works well.

The 2-ClEtNH2 might polymererize, plus it will react with the product to form oligomers. That is why most people use mono-protected amines for these reactions or maybe Boc or Cbz-amino-ethylchloride instead, that might be stable to the conditions you suggested.

Waffles SS - 23-12-2013 at 09:05

Thanks Dr.Bob ,
Do you have detail for that reaction(Buchwald RXN on 1-naphthylbromide with ethylenediamine)?
What about 2-Nitroethylamine?
Reaction of 2-Nitroethylamine with 1-naphthylchloride and then reduce NO2 to NH2 by Fe/HCl?

DJF90 - 23-12-2013 at 09:20

How about conjugate addition of the 1-naphthylamine to 1-nitroethylene, followed by reduction of the nitro group?

Waffles SS - 23-12-2013 at 09:27

@DJF90 that is interesting.
Quote:



Wiki

DJF90 - 23-12-2013 at 14:41

The requisite nitroethylene can be made by dehydration of 2-nitroethanol with phhalic anhydride. OrgSyn mentions this in the discussion section of 2-nitroethanol, which is formed from formaldehyde and nitromethane by Henry reaction. If I'm not mistaken, a procedure for 2-nitropropylene is also given in OrgSyn, and the dehydration step in particular is explicitly described. It ought to be applicable to the nitroethylene prep too.

Regarding storage of the nitroethylene: I recall something saying a 10%w/w solution in benzene keeps well at 10*C. I'm sure you can find the appropriate paper for the finer details.

Waffles SS - 23-12-2013 at 21:59

Thanks DJF90,
What about imidazolidinone?
As @PHILOU Zrealone mentioned this is possible to selective alkylation of Ethylenediamine by Imidazolidinone
http://www.sciencemadness.org/talk/viewthread.php?tid=25527#...

In this case we just need to attach one Naphthalene to one of the Nitrogen on Ethylenediamine(reaction of Naphthyl Chloride or Bromide with Ethylenediamine) and i dont know this is possible or not.

UnintentionalChaos - 23-12-2013 at 23:15

There's also this: http://www.orgsyn.org/Content/pdfs/procedures/cv9p0636.pdf

Nitroacetaldehyde diethyl acetal which would probably readily condense with 1-naphthalamine to N-(1-naphthyl)-2-nitroethanimine. A serious dose of reducing agents would bring about the desired product (perhaps in two steps, something mild to reduce the imine followed by something stronger to reduce the aliphatic nitro group.)

[Edited on 12-24-13 by UnintentionalChaos]

Waffles SS - 24-12-2013 at 09:43

thanks @UnintentionalChaos ,
one of my friend suggest below method :
Quote:

Starting from 1-aminonaphthalene and glycolaldehyde, you make 2-(Naphthalene-1-ylamino)-ethanol via reductive alkylation with STAB (sodium triacetoxyborohydride).
Second step, chlorination with thionyl chloride, gives you (2-Chloro-ethyl)-naphthalene-1-yl-amine hydrochloride. Use low temperatures (not higher than room temperature) here to avoid self-condensation and an excess of thionyl chloride.
Third step, reaction of the hydrochloride with a hefty excess of conc. ammonia solution (approx. 500-1000 fold molar excess, but ammonia is dirt cheap; use a 1:1 mixture of alcohol and strong ammonia) yields your desired N-(1-Naphthyl)ethylenediamine. Instead of the fast method with ammonia, you could also use the Delepine or the Gabriel reaction, but I leave this choice up to you

DJF90 - 24-12-2013 at 09:55

Seems reasonable.

Waffles SS - 25-12-2013 at 09:38



What about reaction of Ethanolamine-O-sulfate(2-Aminoethyl hydrogen sulfate) with excess 1-Naphthyl amine?
Quote:


2-Aminoethyl hydrogen sulfate prepare by Esterification of Ethanolamine (H2N-CH2-CH2-OH)with sulfuric acid.

PREPARATION OF 2-AMINOETHYLSULFONIC ACID
Galuh Widiyarti*), Muhammad Hanafi, Siti Isnijah, L. Broto Sugeng Kardono, Ermawan,Ngadiman, and Andini Sundowo




[Edited on 25-12-2013 by Waffles SS]