Sciencemadness Discussion Board

Substituting hydrogens in hydroxylamine

Eddygp - 15-9-2013 at 13:04

I had been thinking for a while about hydroxylamine, NH2OH, and about the possibility of substituting the amine's hydrogens (not the hydroxyl one) by any R group. This would yield things like N(CH3)2OH or, in general, NRR'(OH). EDIT: Not ketoximes, because I don't want to use that carbon double bond to the nitrogen!!
I would like to see if it would be easy to do so from scratch, or with techniques available to home chemists (that is, not using a palladium catalyst heated up at 820K under 2.3 atm of pressure).
Just curious about it.
EDIT: Uploaded an image of a possible compound:

[Edited on 15-9-2013 by Eddygp]

truc.jpg - 20kB

AndersHoveland - 15-9-2013 at 21:17

I have previously been thinking about the easiest routes to N,N-dimethyl hydroxylamine, because I think it could form very stable and very powerful explosive salts (particularly the nitroformate).

Would bromomethane add methyl groups to hydroxylamine? If the hydroxyl group got methylated, could that not just afterwards be hydrolyzed off with acid?

Typically the routes to hydroxylamine derivatives do not start with hydroxylamine.

One lab preparation I saw was oxidation of N,N-dimethyl-cyclohexylmethylamine with H2O2 to the N-oxide, then pyrolysis at 160 C, releasing the dimethylhydroxylamine, and leaving an unsaturated methylenecyclohexane.

Eddygp - 19-9-2013 at 12:40

Beg my scarce and sparse knowledge, but I think that the bromomethane would probably alkylate the hydroxyl group instead.

DraconicAcid - 19-9-2013 at 13:49

Quote: Originally posted by Eddygp  
Beg my scarce and sparse knowledge, but I think that the bromomethane would probably alkylate the hydroxyl group instead.


Not sure about that- nitrogen tends to be a better nucleophile than oxygen.

Eddygp - 21-9-2013 at 00:27

Oh, my bad! That is true, DraconicAcid! However, it might not react evenly giving either N,N-dimethylhydroxylamine or N-methylhydroxylamine... even with stoichiometric proportions it would reach at a certain point an equilibrium. A catalyst or a temp. change would be needed then, drawing the equilibrium to the product. After that something should be added to react with the hydroxylamine but not with the product.