N-Methylhydroxylamine...Can it be used?

[sYnThOmAtIc]

I found a synthesis for this compound the other day in an old organic preparations book.. It is the synthsis of
N-methylhydroxylamine from nitromethane and zinc. I can post it later if anybody is interested. So can n-methylhydroxylamine be used as a direct replacment for hydroxylamine in teh oxime formation?

From: High-yielding synthesis of MDA from MDP2P
via Formation of the Oxime Followed by Reduction Step 1. Formation of the oxime.

5.4g sodium acetate trihydrate and 4ml water was combined in a 50ml round-bottomed flask. The mixture was heated gently with stirring until the acetate was in solution. 20 ml MeOH was added followed with 4.5g MDP2P. To this there was added 2.3g hydroxylamine hydrochloride and the mixture was refluxed with stirring for 1.5h. After this period 10ml water was added and the heating source was removed and the mixture was allowed to cool in a waterbath with the stirring continued. After returning to room temp the flask was put in the freezer for an hour or so. The white crystalline material was filtered and washed with 50ml water (the filtrate may turn cloudy as small amounts of product crystallizes). The product was dried over magnesium perchlorate to constant weight.

Yield: 4.5g (92%), mp 84-85°C. Lit: 84-87°C (H2O-EtOH)



The reference the book uses for the synth is: Beckman, Ann., 365, 205 (1909).   J. Scheiber, Ann., 365, 225 (1909).

[hypo]

obviously you wouldn't get the oxime, but an enamine.

[sYnThOmAtIc]

I guess I'll go have to learn about oximes and enamines. In the mean time, assuming one used the n-methylhydroxylamine in place of hydroxylamine in that synth to the end, would it give mdma instead of mda?

[Rhodium]

It depends on the reducing agent. If using a rather vigorous reducing agents you will get MDMA, but milder agents like BH₃, NaBH₃CN or NaBH(OAc)₃ will allow you to end up with

FLEA

(http://www.erowid.org/library/books_online/pihkal/pihkal081.shtml)
(Note that Shulgin isn't isolating the intermediate enamine in his procedure, as it is likely to be unstable).



The enamine may also take on the resonance form of a nitrone (as indicated by Shulgin), and its double bond is instead between the nitrogen and the side chain (just like the oxime) and has a positive charge on the nitrogen and a negative charge on the oxygen.