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Author: Subject: Diisonitrosoacetone
Sauron
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[*] posted on 29-11-2007 at 19:52


Ber. articles prior to 1902 are freely available at Gallica. You have to call them up page by page and email them to yourself. Tedious but free.

http://gallica.bnf.fr/Catalogue/noticesInd/FRBNF32711339.htm...

Anyway I think I have this one already; and it is probably easier for me at the moment to get it from Wiley than to find it in the haystack of my pile of CDs with such material.

So hang on and Sauron will provide.



[Edited on 30-11-2007 by Sauron]

Attachment: Ber21_2989.pdf (241kB)
This file has been downloaded 721 times





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Axt
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[*] posted on 3-12-2007 at 23:34


Thanks Sauron, heres the translation from that article of the preparation of trioximinopropane, provided by grind.

Heat pure Dinitrosoaceton with 7-8 times the amount of water and the equimolar amount of NH2OH x HCl and AcONa 1-2 hours at 50-60°C. After some hours of standing the trioxim appears in brown, hard crystals. For purification the crystals are crushed and crystallized several times from water, possibly with addition of charcoal. Slow cooling down produces a special form of crystals (I have no translation for it), quick cooling gives a colorless powder of crystals. Scratching with a glass rod forces crystallization.
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Sauron
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[*] posted on 4-12-2007 at 01:45


Thanks, sounds pretty straightforward.

The calculated amount of hydroxylamine for one equivalent, I assume, to react with the carbonyl.




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S.C. Wack
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[*] posted on 16-8-2009 at 11:51


You never have to download Gallica articles one page at a time and email them to yourself - not now, not then, not before. Whole volumes or a specific number of pages starting with a specific page are no problem. Email, WTF?

Back to acetonedicarboxylic acid, I see that Beilstein (Hauptwerk) mentions the vague patent DE32245 pretty similar to von Pechmann's article, applied for a few days after the Ber. article was submitted. It also mentions a French article available at Gallica where citric acid was oxidized with KMnO4, but that one may not be too useful, certainly not as written.
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[*] posted on 17-9-2010 at 14:47


Let me refer your attention to the same topic in the organic chem section:
"diisonitrosoacetone can condense with hydroxylamine to form
1,2-dinitroso-propyl,2-oxime.

It is called "nitroso" because that is the demoninant tautomer at neutral conditions.
Making it basic, the oxime tautomer dominates, and this is what can act as an acid.
O=NCH2C(=O)CH2N=O and HON=CHC(=O)CH=NOH

1,2-dinitroso-propyl,2-oxime can act like a triple acid, forming salts with the -3 anion,
(-)ON=CHC(=NO(-))CH=NO(-)

1,2-dinitroso-propyl,2-oxime could either be reduced with bisulfite to give a decent yield of propyl trihydroxylamine, or oxidized with NO2 bubbled in to form real "nitroglycerin", with 3 nitro groups instead of nitrate."

Sorry, wanted to put the post here, outside from obscurity in the organic chem section, but too late to delete the other post.
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Boffis
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[*] posted on 7-11-2011 at 07:14


@Axt

Please could you repost these links as I can't get access to them or could you contact me via U2U. I am working on diisonitrosoacetone and would be interested to read them, I am also interested in nitrolic acid type compounds:

http://www.sciencemadness.org/talk/viewthread.php?action=att...

http://www.sciencemadness.org/talk/viewthread.php?action=att...

http://www.sciencemadness.org/talk/viewthread.php?action=att...

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PHILOU Zrealone
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[*] posted on 11-11-2011 at 12:35


Maybe a good way to the same kind of compounds can be via.
1°) glycerol (propantriol) + HCl --> 1,3-dichloropropan-2-ol
HOCH2-CHOH-CH2OH + 2 HCl --> ClCH2-CHOH-CH2Cl
The later can then be reacted with NaCN to provide N#C-CH2-CHOH-CH2-C#N
Maybe direct reaction with HNO2 (as it happens with activated CH in alfa of nitriles) will lead to:
A) N#C-C(=NOH)-CHOH-C(=NOH)-C#N
B) N#C-C(=NOH)-CO-C(=NOH)-C#N (if HNO2 oxydises the alcool funtion)
C) HON=CH-CHOH-CH=NOH.2 NH3 (diamonium salt)(if nitriles are hydrolysed into ammonium carboxylate and subjet to spontaneous decarboxylation)
D) HON=CH-CO-CH=NOH.2 NH3 (if HNO2 oxydises the alcool funtion and if nitrile hydrolysis and decarboxylation occurs)

2°) Via oxydation of 1,3-dichloropropan-2-ol into lacrymatory 1,3-dichloropropanone (which is also accessible via aceton chlorination under specific conditions (see Wargas book at the bottom of the SMF library))
ClCH2-CO-CH2Cl can the be reacted with NaCN to yield N#C-CH2-CO-CH2-C#N (1,3-dicyanopropan-2-one).
After acidic or basic hydrolysis in the cold this would deliver HO2C-CH2-CO-CH2-CO2H.




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AndersHoveland
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[*] posted on 7-1-2012 at 02:25


Possibly acetone could be reacted with a nitrite ester?

I found this, which shows that a nitrite ester can react with
R3C-CO-CH2-R to form an oxime, R3C-CO-C(=NOH)-R,
where R is a non-hydrogen alkyl group,
http://en.wikipedia.org/wiki/File:Camphor-Isonitrosocamphor....

Not sure what the reaction using acetone would be, however, since there is an additional hydrogen atom that could potentially be oxidized. I suspect the reaction of the nitrite ester with the ketone proceeds through the enol tautomer, in which case the ketone would be less liable to enolize after the addition of an oxime group because that would involve a carbon atom being double bonded on both sides, which is not favourable.
CH3-C(OH)=C=NOH

But, as we know, an oxime can potentially transiently tautomerize to a nitroso group. This could potentially allow ketone to enolize again, with subsequent further oxidation. I am not sure what would result, perhaps some sort of nitrolic acid. Ideally, however, the reaction rate of formation of oxime would be greater than the rate of further oxidation of oxime, such that decent yields of dinitrosoacetone might possibly be obtained. As the tautomerization of oximes of aldehydes (as opposed to ketones) to nitroso groups has a lower equilibrium (because the oximes of aldehydes tend to trimerize), this is likely to be true.

[Edited on 7-1-2012 by AndersHoveland]
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