A Crazy Idea... (Reactions with NX3)

[MrSamosa]

A crazy idea came to me the other day... Normally we think of NX3 compounds, such as Nitrogen Triiodide as too unstable to think of and a waste of chemicals to synthesize. For the most part, this is in fact true. However, have you ever considered the potentially powerful halogenating properties of such compounds?

Think about it... on their violent decomposition, they release heated Halogen fumes. Therefore, I see a chemical such as NCl3 as a potential Chlorinating agent, if measures are taken care to minimize its handling and it is only produced as needed. Do you suppose that such compounds could be used as substitutes for PCl3 or PI3 in certain reactions?

I can find very little information regarding such compounds, and most of it is from the Anarchist Crapbook. I did find a neat little site whose author did experiments on the stabilization of NI3, but had little success. It is for this reason that I am interested- because nobody has dared to try it. It is that bit of mystery that excites me :) .

[Mr Cool]

Hmmm.... isn't there a method in which NCl3 is made from AN solution and chlorine gas?
What I am imagining is some AN solution, floating over DCM or other dense, inert non-polar. Chlorine is allowed to react with the AN, NCl3 forms and sinks to the bottom of the AN solution, where it meets the DCM and dissolves.
Thus it never has to be handled in the pure form, only as a dilute solution.

[jfk]

isnt Phosphorus very rare and hard to come by?

[blindreeper]

SWIM gets R phosphorus from match box sides. Very kewl cause there is about 0.1g of red P on each box but hey 100 boxes = 10g. And how much does a 10 pack of matches cost you? 2 - $3

[Marvin]

Inorganic synthesis has a method for producing a dilute solution of NCl3 in organic solvent, I think carbon tet. Its fairly stable but very slowly evolves phosgene on standing.

Ive also read a few suggestions in the literiture about using NCl3 as a chlorinating agent, mainly while I was trying to find out more information on it. Its certainly useful, but I failed to see any advantage over existing chlorinating agents. No specific reactions were given in what I read, only fairly theoretical arguments based on its decomposition. I have the feeling, that if it were a suitable replacement for phosphous chlorides that it would react rather more rapidly with water than it does.

Theres always sulphur chlorides as an alternative. They arnt pleasent to handle, but then neither is NCl3.

[drednort]

I dont think they're a good source of halogen.
Most of the NX3s are pretty unstable and a bit tricky to use.
But I remember that NCl3 can be used in reactions, when dissolved, and when you hydrolyse the product it substitues a NH2 onto a tertiary C-H bond for you. Not great yields but otherwise difficult reaction. So, to answer your question it is more likely that they're better for difficult aminations.

[MrSamosa]

Yes, NX3 compounds are indeed tricky to use... But, I'm sure we all like a bit of adventure- why else would we be at Roguescience?? ;) .

I like the idea of it being dissolved in the Dichloromethane, because that is a readily obtainable solvent. But what about NI3? Indeed, that is even more unstable than NCl3, but still - the purpose of my interest in these compounds is for their possible use in Halogenations (save for NF3, which is quite stable); not just Chlorinations in particular.

Could NCl3 or NI3 perhaps be used in synthesizing Phosphorus Trichloride or Phosphorus Triiodide, respectively? I don't see much of a purpose for doing it this way, since Cl2 or I2 could be added directly to the Phosphorus instead of the Nitrogen first...but just out of curiosity :) .