Reduction of PN2P with Zn/Hg

[Rhodium]

I have read the whole article, and I still don't catch your drift. That a reaction works with nitromethane and chloropicrin (trichloronitromethane) is one thing, as both are nitro compounds - can you please write in detail how you are thinking instead of referencing different documents which still does not explain what I'm asking?

I's too bad that people haven't used my paraformaldehyde method, as by using that and recycling any precipitated ammonium chloride, the methylamine yield from HMTA varies between 55-60% of theory.

[Organikum]

in organic chemistry up to now. So I dont bother with the "why" chief. I did what the old chemists did - I tried it. There is this wellknown german patent from 1898 for the hexamine reduction using zinc and ambient temperatures (or below I want to add).
There they tell to use the "necessary amount of zinc and HCl".
Hm. This already made me guess the secret is hidden in either the amount of HCl or the amount of Zn to use. They tell to use 2liters water on 100gram hexamine - which for me correspondeds with the old french article where it was told that the reaction proceeds in the way told - producing methylamine and CO2 - as long sufficient water is used. Both made me guess that "enough water present" is more than theory tells.
Putting both together and the information on Fe/Zn-HCl reductions working in another way as thought whereby MUCH LESS HCl is necessary I got to the point I am now. (and thats the essence of the Krause-article, it plain tells that the reactions of the reducing agent are complete different from the theory applied before and this is absolute independent from the substrate on which the reducing agent is used on).

If you cannot see it in the articles - try it.

I will post the complete translation of the Krause article later this week.

But meanwhile I believe this stuff is either disliked because it is posted by me or because on this board discoveries which are of practical use in clandestine OTC-chemistry are not wanted anymore - the Krause reference is a find of the same importance as the Al/Hg reductive amination was. Thanks to lugh for digging it up.

Paraformaldehyde isnt OTC in most countries - plain hexamine is.

[SpicyBrown]

Well regardless of the theory involved, I for one am eagerly awaiting your translation Organikum.  

-SpicyBrown

[Organikum]

The translation is almost finished - sorry for the delay, I am computertechnically hindered these days so simple tasks take a long time.  

But a humble question to Rhodium:
you wrote:

as both are nitro compounds

referring to nitromethane and chloropicrin

A nitro compound is a compound containing nitrogen - right?
And we would like it being reduceable to methylamine?
A compound which contains nitrogen and is reduceable to methylamine?
Hey: HMTA !

(at least those ancient germans call the Zn/HCl process in their patent from 189X a "reduction". Btw: Those ancient german patents have the advantage that in those days patents got deleted after some time if the use of the patented methods in industry wasnt proofen by the patentholder)

[Rhodium]

A nitro compound is a compound containing nitrogen - right?

No, a general nitrogen-containing compound is called nitrogenous in english, while nitro compounds only refer to those compounds which can be written as R-NO₂ and sometimes even as stringent as R¹R²R³-C-NO₂ (this to exclude nitrate esters such as R-O-NO₂).

[bio]

I for one agree with you. Seems most want to complicate things with all types of new fancy expensive reagents when the simple old stuff often works better. I'm sick and tired of separating the NHCl and Me2NH from the formaldehyde product. Now if I could only find a simple Baeyer/Villiger ketone oxidation catalys instead of all the Rhenium whatever bullshit I would be happy. No library around here for research so I'm stuck with just the internet. Thanks for the info on the Vibra Stirrer. I have the Vogels but just forgot  what it was. I'm building a little one for an electrolysis cell.