Methylenediisonitramine

Carefully read US1625966 page 1 lines 53 to 81

MEDNA will form explosive salts with; Barium, Cadmium, Calcium, Cesium, Copper, Iron, Lead, Mercury, Potassium, Rubidium, Silver, Sodium, Thallium, and Tin. I have read MEDNA will form a salt with Monohydroxylamine but I’m not sure.

I will hopefully be attempting the Sodium, Calcium, Lead and Barium salts this weekend. I finally found a use for 2½g of barium.

To synth the Barium salt react Barium Chloride in a solution of the (Na)MEDNA salt. Filter and dry the precipitated (Ba)MEDNA. The Barium salt is noted to be the weakest of the MEDNA salts.

The Calcium salt is formed in the same way as the Barium salt. Calcium Chloride is added to a solution of the Sodium salt and the precipitate is filtered and dried.

Attached is an extract from an article titled "The Ultraviolet Absorption Spectra of Aliphatic Nitramines, Nitrosamines and Nitrates" Its related to determining the difference in spectra between MEDINA & MEDNA. This isnt of great practical value to us, but one sentence caught my eye which states:

<i>"The Traube compound is unstable in the free state and is usually prepared as the mono-ammonium salt or the disodium salt."</i>

One of the German articles above gives the syth of the ammonium salt, however derived from its Ag salt, this route has little value. The above quote suggests that the ammonium salt can be made without going through the sodium, silver salts, NH₄-MEDNA should be a useful HE. Only known comparisons are with the MEDINA salt:

NH₄-MEDINA is listed in PATR as being 142% power of TNT, where MEDINA is 154-158% and RDX is 150% on the ballistic mortar test. (Vol. 2, B 266)

Experimental:

Into 80ml acetone in a 100ml measuring cylinder was bubbled 100ml 70% HNO3 worth of NO (though tubing was leaking) by the reaction with copper pipe. The solution remained clear and seemingly unchanged.

The copper nitrate solution was poured out, and flask charged with ammonium nitrate and sodium hydroxide as to generate ammonia gas. This gas was fed into the acetone solution and an immediate white precipitate formed, hopefully the ammonium salt of the intermediate of MEDNA, but possibly just NH4NO3.

The Acetone was decanted, water was added and the precip dissolved readily. This was then precipitated with Pb acetate to make sure that it was not NH4NO3 (from HNO3 fumes coming over from the gas generator). Since it precipitated, it wasnt a nitrate salt. The lead precipitate is now drying (though it was just rained on )

Hopefully it will show the properties of Pb-MEDNA, thus giving a higher yielding syth for both the secondary HE from ammonia and the primary from lead salts.

[Edited on 17-3-2005 by Axt]

Attachment: medna-spectra.pdf (664kB)
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a nitric oxide preparation using sodium nitrite instead

Thanks for the very interesting article .

Did you already have this article before starting this thread ?

It sheds more light on this interesting reaction and
somewhat resolves any confusion about the matter of the sodium ethoxide requirement by the declaration
that sodium hydroxide works just as well . But I wonder if it works just as well with other conditions being equal . It is terrible that the details of experiments
which indicated the equivalency of NaOH with the ethoxide were not shared , but simply mentioned in passing .

That equivalency observation possibly destroys the original hypothesis for the mechanism of the reaction ,
and an added indication of this is provided that the reaction also proceeds in methanol . However , I have some question about whether that equivalency is an unqualified observation . It could be that the reaction proceeds differently under different conditions . It may be that in an unpressurized apparatus that the sodium ethoxide in ethanol is the best way to go as it would seem likely to be more reactive .

Also interesting that this is a fairly recent publication ,
from six years ago .

A side note here in the " thinking out loud " category
I have been wondering if there might be a reaction between
trimeric acetone peroxide and R-salt in methanol , or if
R-salt dissolved in plain acetone might react with the solvent
on long keeping , perhaps at elevated temperature or
with some slight acidification or added catalyst . I keep thinking that some sort of nitric oxide donor in solution
would be more convenient than working with gas generators and bubblers , and could lead to the same or similar compounds . Organic nitrite esters would also seem to
be a possibility here as such nitric oxide donors . Perhaps
even nitrosyl sulfuric acid , or some sort of aromatic nitrososulphonic acid? could have usefulness in some reaction scheme of this general sort . There is a lot of food for thought and unexplored territory where these sorts of
reactions are concerned .

[Edited on 2-9-2006 by Rosco Bodine]

Nah, I only come happened across them a few weeks ago. Knowing what to search for helps, considering the powers that be decided on a new name/structure.

Also considering how recently the reaction, if pushed, has shown to produce the tris(diazeniumdiolates). Wonder if its possible to push nitromethane all the way to produce sodium nitromethanetris(diazeniumdiolate) CN7O8Na3. That'd be interesting.

[Edited on 2-9-2006 by Axt]

Page 4 of the article just above is saying exactly what I have been thinking as regards to nitrosyl " donor " scenarios ,
already thought about nitrosyl chloride too ......
and indeed one of the things I had thought of was adding
an organic nitrite to an acidified alcohol / acetone solution
at low temperature . Good stuff being added here with these new references . Hopefully this is leading to some refined methods . Reference #39 would be interesting there .

BTW , nothing like 16 pages of " light reading " having 302 references ......
my eyes began to cross and my brain
went into " scan mode " on about page 5 .....
How about the rest of you ?
Nerds rule , that's for damn sure .

A rose by any other name ....
but indeed the nomenclature changes
get hard to follow when researching for the
old name , unless the change is conspicuously noted ,
and cross-referenced also to the old name in the
newer references . Also noticed the archaic " gr. "
abbreviation for *grams* in the older patent .

The #13 reference in the University of Wyoming paper
could be interesting also . I need to get a password for
the references thread . If anyone has access to that
Canadian Journal of Chemistry article please attach it here in this thread .

George , Kierstead , and Wright , Can. J. Chem 1959 , 37 ,
679-699

[Edited on 2-9-2006 by Rosco Bodine]

Dont think you'd have anything forming in acid solution. Unless I've read something wrong your target compound would be the one donorin'

Yeh, the chem. rev. article gives some other nice possibilities, particularly the N-diazeniumdiolates. Though I cant think of any easily accessable secondary amines, I'd probably start at glyoxal-ethylendiamine condensation, then try react that in place of acetone hoping for .... eh, the damn ugly sounding "sodium decahydropyrazino[2,3-b]pyrazine-1,4,5,8-tetrakis(diazeniumdiolate)". Really gotta think up a better name, PPTDD will do or how'bouts tetraisonitraminopyrazinopyrazine.

What other secondary amines are available and offer acceptable OB? most urea derivatives wont be soluble in alcohol.

[Edited on 3-9-2006 by Axt]

On page 4 of the Hrabie and Keefer article , is the relevant sentence for this use of organic nitrite , see left column under " 1. nitrosations " , second paragraph , third line below the reaction product (1) , quote:

" Organic nitrites can also be used under acidic conditions to produce the " free acid " (O2-protonated) form of the diazineiumdiolate directly , 39 although this is usually accomplished via reaction with acidified inorganic nitrite " ......

[ my note: such as NaNO2 + HCl , see the next diagram in the article for reaction product(2) ]

That was exactly what was the source of my interest in reference #39 , but it seems that #reference is a misprint in the article , because the actual article relates to nitrosation of methylhydrazines using NaNO2 . With only 302 references
you would think they could keep 'em all straight

But anyway it is also mentioned in that second Chem Review article which in different words will say the same thing , and
agrees with what is my thinking and what I was meaning
concerning the use of organic nitrites , that an organic nitrite
is going to serve the same function in a solvent reaction system when acidified , as does NaNO2 in an aqueous system when acidified ....forming HNO2 in situ , and N2O3 ,
( NO + NO2 ) thereby acting as a source of NO which can
be " cherry picked " by receptors on the target compound
from that " stew " , as can any of the other nascent products
which may react . Also for the organic nitrites which are
easily hydrolyzed , simple contact with moisture in the solvent can do the same thing , the byproduct of the
decomposition of ethylene glycol dinitrite , being ethylene glycol for example . In another thread on ethylene glycol dinitrite I have posted some observations concerning
the behavior I have observed concerning the instability of
the organic nitrites to acids which has to be taken into account during their synthesis / separation , and has bearing on their usefulness in synthesis . The direct transfer of the nitrosyl group from the organic nitrite ester is called
" transnitrosation " by the authors of that second Chem Review article , and it is a parallel to the already observed
" transesterfication " reaction which is more commonly known .

Quote:

Yeh, the chem. rev. article gives some other nice possibilities, particularly the N-diazeniumdiolates. Though I cant think of any easily accessable secondary amines, I'd probably start at glyoxal-ethylendiamine condensation, then try react that in place of acetone hoping for .... eh, the damn ugly sounding "sodium decahydropyrazino[2,3-b]pyrazine-1,4,5,8-tetrakis(diazeniumdiolate)". Really gotta think up a better name, PPTDD will do or how'bouts tetraisonitraminopyrazinopyrazine. What other secondary amines are available and offer acceptable OB? most urea derivatives wont be soluble in alcohol.

At this point I am in " structure shock "

Some of these compounds are beginning to look like they
are computer conceived and generated .....like little robots
needing motors to animate their many little legs so that
locomotion can be achieved Plug these little rovers in
and watch 'em go

I read a few pages from those Chem Review articles ,
and I got tired and fell asleep .....I must be getting too old for this stuff . I looked at those photos of Hrabie and Keefer
and laughed out loud knowing that those are " glamour shots " for press release and publication , thinking that the
photos were taken before this research paper was written ,
and wondering what those fellows must *really* look like now , sort of like Linus Pauling did after too many years of way too much Vitamin C , and not enough beer and poon tang , smiling just like he still had good sense , and too
worn out to know the truth it was over

BTW , in that second Chem Review article on page 6 , right column , under 1. synthesis , halfway down in the first paragraph is something interesting . quote:

" Recently it was reported that alkyl nitrites could be synthesized from the reaction of alcohols with gaseous NO in the presence of air , where nitrous anhydride ( N2O3 ) , generated in situ , likely serves as the nitrosating agent . 105 "

It would be my expectation that bubbling the NO through
hydrogen peroxide would also produce the N2O3 even more
effectively . The big * if * here of course being , it could
also oxidize the NO all the way to nitric acid , but I am expecting with dilute H2O2 , it won't go that far .

This should provide an additional method for synthesis of organic nitrites which could utilize the reaction I posted on the first page of this thread :

Nearly pure Nitric Oxide , ( NO ) , can also be prepared by heating a mixture of K nitrate , Ferrous Sulfate , and dilute sulfuric acid . PATR , vol. 8 , page N-129 .

2 KNO3 + 5 H2SO4 + 6 FeSO4 ---->
3 Fe2(SO4)3 + 2 KHSO4 + 2 NO + 4 H2O

By further oxidizing the NO produced from this reaction to N2O3 by bubbling through hydrogen peroxide , a path to nitrites is provided . Bubbling the N2O3 into an aqueous solution of an alkali base would provide the alkali nitrite . Bubbling the N2O3 into an alcohol would convert it to the
nitrite ester .

Haven't tested the peroxide conversion ...but this could be a very useful lab method for nitrosations , diazotizations .

Serendipity strikes again !

( and hopefully not " senility " instead )

It sure beats the hell out of Murphy's law .

[Edited on 3-9-2006 by Rosco Bodine]