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Axt
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| Quote: | Originally posted by Rosco Bodine
Reference #39 would be interesting there .
The #13 reference in the University of Wyoming paper
could be interesting also .
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#39 of chem. rev. is attached along with a couple others. I think #13 will only be available offline.
Attachment: diazeniumdiolates and NO donors.zip (1.2MB)
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Rosco Bodine
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| Quote: | Originally posted by Axt
| Quote: | Originally posted by Rosco Bodine
adding an organic nitrite to an acidified alcohol / acetone solution at low temperature. |
Dont think you'd have anything forming in acid solution. Unless I've read something wrong your target compound would be the one donorin'
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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.
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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]
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Axt
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Was looking at "potassium dinitrososulfite" in Brauer (pg. 504). Looked up its structure [attached] and its analogous to the subject of this thread.
<center><img src="http://www.sciencemadness.org/scipics/axt/potassium-dinitrososulfite.jpg"></center>
Could be a simple and interesting thing to try, if only due to the analogy as I dought its explosive properties are of any interest ( Brauer says
"explodes upon heating").
If I was to try it I would:
Heat copper powder and concentrated sulphuric acid to generate sulphur dioxide.
<b>Cu + H2SO4 -> CuSO4 + SO2 + H2O</b>
Bubble sulphur dioxide through aqueous potassium hydroxide forming potassium sulphite solution.
<b>SO2 + 2KOH -> K2SO3 + H2O</b>
React copper pipe with dilute nitric acid forming nitrogen oxide.
<b>3Cu + 8HNO3 -> 3Cu(NO3) + 2NO + 4H2O</b>
Bubble nitrogen oxide through potassium sulphite to precipitate "potassium dinitrososulphite".
<b>K2SO3 + 2NO --> K-O-SO2-NO=NO-K</b>
[Edited on 23-9-2006 by Axt]
Attachment: Infrared Spectra of the Salts of the Dinitrososulfite Ion (Nitrosohydroxylaminesulfonates).pdf (259kB)
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Axt
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Carrying on with the analogies, sodium trioxodinitrate is structurally simular. Na-O-NO=NO-Na could be regarded as the parent acid to the
diazeniumdiolates.
<i>"Synthesis of Na2N203. Crystalline Na2N203 was prepared by the modification of Angeli's synthesis described by Hunt, et al. i.e. by reaction
between NH2OH and C4H9ONO2 in absolute methanolic solution containing NaOCH3. Reactions were carried out at 0° under N2, and best yields were
obtained with NH2OH in stoichiometric excess and with very long reaction times. Products were repurified by solution in minimum volume of H2O and
reprecipitation by addition of CH3OH, with attendant loss such that 30% could be counted a good yield. The precipitate was dried in vacuo at 120° and
stored under nitrogen in a drybox."</i> Inorganic Chemistry, Vol. 14, No. 3, 1975 [attached]
[Edited on 22-9-2006 by Axt]
Attachment: thermal decomposition of oxyhyponitrite.pdf (1.1MB)
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Rosco Bodine
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I wonder if an ammonium dinitrososulfite would form as well as the potassium salt , and if so , then perhaps a tetraammonium copper dintrososulfite
could form as well .
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Axt
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The ammonium salt is mentioned in the article attached above. The sodium salt was "suprisingly soluble" allowing the other salts to be precipitated
from its solution.
<i>"The ammonium salt was prepared by a metathesis reaction based on the insolubility of ammonium dinitrososulfite relative to the sodium salt.
In this procedure excess ammonium chloride and ammonium hydroxide are added to the reactants used to prepare the sodium salt. The crude ammonium salt
precipitates out as the reaction proceeds. The salt is purified by methods previously described. The potassium salt can also be prepared by a similar
type reaction."</i>
It may show some interesting solubilities, perhaps a hydrazine salt would also precipitate readily, as well as its Cu complexes. Though all its
complexes have a rather dismal OB (it is already 0%OB), still may be a novelty like the persulphates.
[Edited on 23-9-2006 by Axt]
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Rosco Bodine
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Phosphites could possibly react similarly to form
a dintrosophosphite .
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Zelot
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Does the reaction to make MEDNA have to use NO, or could you use N20 in its place?
I don't have access to nitric acid (dilute or otherwise), but I do have ammonium nitrate. Couldn't
you just decompose ammonium nitrate into water and N20, and bubble that through the acetone/sodium ethoxide mixture?
[Edited on 3/22/2008 by Zelot]
So... what did you do over the weekend?
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