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Topic: Amine to nitrene?  (Read 5593 times)

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Offline HP

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Amine to nitrene?
« on: February 14, 2006, 02:04:40 PM »
Hi men,
Do someone know how could aliphatic amine be converted to azide(RNH2-->RN:  ???
I found some reaction schemes for preparing alkyl nitrene where was ilustrated that amine can directly be oxidized to nitrene but it wasnt mentioned the oxidizing agent for that purpose...If someone have some idea pls help me.
Thanks!
xpp

Offline HP

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Re:Amine to nitrene?
« Reply #1 on: February 14, 2006, 03:50:44 PM »
 Nitrenes are uncharged, electron deficient molecular species that contain a monovalent nitrogen atom surrounded by a sextet of electrons.In my post i mean that compounds not the shown by you synthesis of imines. Conventional methods for synthesis nitrenes is from alkyl or aryl azides(R-N3)
by heat or photochemical activation.Also from N-chloro(or bromo)amines RNHX with Base elimination...
But my question is which oxidant could be used for the reaction:
R-NH2 + oxidant?-->R-N::
xpp

Offline Albert

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Re:Amine to nitrene?
« Reply #2 on: February 14, 2006, 04:23:10 PM »
What about nitrous oxide as oxidizing agent? Maybe working at high temperature and with basic conditions.

Offline HP

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Re:Amine to nitrene?
« Reply #3 on: February 15, 2006, 12:29:38 PM »
I dont know..i havent read anything about the possible oxidizing agents using this route resp the reaction conditions. If someone have such information this problem i'll deeply appriciate it :)The only thing i could mention is that this reagent(s) should react with both NH2 protons may be water byproduct  ??? Continue searching...
xpp

Offline HP

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Re:Amine to nitrene?
« Reply #4 on: February 17, 2006, 03:29:36 PM »
Hi again,
I found some articles descrbing some Cu and Fe salts as oxidizing agents for nitrene generation. Also interesting is Pb(Ac)4 - i dont know the exact name this plumbium salt...In fact may be better route for making nitrenes is those starting from the N-halogene derivatives of the corresponding amines. For example N-chloro or bromoamines. But how to easily synthesyze them  ??? I know that amines react with Cl2 gas in the presence of Na2CO3 to obtain N-chloroamines. Do you think this reaction may occur with elemental Br(Br2) or with bromine water and amines ? What about reaction with iodine(J2) or NaOJ and how stable are N-iodoamines? Is possible reaction amines with bleach(NaOCl) solution and whats the mechanism such reaction? Sorry for the many questions but tonight have inspiration for asking :)
xpp

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