madscientist
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Dinitrodimethyl oxalate
I believe that dinitrodimethyl oxalate would be a fairly powerful, and fairly sensitive, energetic compound. This is my planned route of preparation:
(COOH)2 + 2CH3OH --(H2SO4)--> (COOCH3)2 + 2H2O
(COOCH3)2 + 2HNO3 --(H2SO4)--> (COOCH2NO2)2 + 2H2O
It would detonate as follows:
(COOCH2NO2)2 --> N2 + 2CO + 2CO2 + 2H2O
It may be well-suited as a booster explosive for less sensitive high explosives.
[Edited on 25-5-2002 by madscientist]
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Nick
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Nice idea...
But I don't think the methyl groups will be very easy to nitrate. I'm not sure why not exactly, that's just the gut feeling I get!
It'd be better, if you can, to use chloromethanol to form the ester, and react the product with NaNO2, to make the dinitro compound by nucleophilic
substitution.
Have you actually heard about this, or is it your own idea?
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madscientist
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It's my own idea.  If the following doesn't happen, then I believe the nitration
of the methyl group, forming a nitro compound, would likely occur.
(COOCH3)2 + 2HNO3 --> (COOH)2 + CH3NO3
I don't think using a nitrite for nucleophilic substitution to prepare a nitro compound will work. There is a distinct difference between a nitro
group and a nitrite group. If I remember correctly...
Nitrite (nitrogen has a valence of three)
--O--(N=O)
Nitro (nitrogen has a valence of five)
--N(=O)2
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madscientist
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Since I unfortunately do not have any methanol on hand, I have begun preparing isopropyl oxalate, which I plan on nitrating tomorrow. I have not been
able to find any information on isopropyl oxalate, even in my chemical dictionary, chemical handbook (extensive data on chemicals and
constants), and all of my chemistry textbooks, except for that it does exist. Hopefully I will be able to reload on methanol tomorrow.
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madscientist
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Something that has just occurred to me: (COOCH2NO2)2 could be used to prepare CH2NO2OH! CH2NO2OH should be acidic; heavy metal salts of this acid
should be interesting (as will be the acid alone)!
(COOCH3)2 + 2NH3 --> (CONH2)2 + 2CH3OH
Therefore...
(COOCH2NO2)2 + 2NH3 --> (CONH2)2 + 2CH2NO2OH
Of course, many other intriguing acids could be prepared this way.
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Nick
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NS with NaNO2 (or, better, with AgNO2) to form nitro-compounds does indeed work. Nitromethane can be/is prepared that way, using methyl chloride or
derivatives thereof and NaNO2. Also, trinitrocyanuric acid is made from trichlorocyanuric acid and AgNO2.
But it won't work for arenes, like TCP.
Hmmm... that acid could be interesting! As could the byproduct, (CONH2)2. It could probably form some nice explosive salts with HNO3 or HClO4, or it
could be dehydrated to to form NC-CN, the hottest burning fuel known!
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madscientist
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Whoops! I forgot about this! The NO2 group resonates between the nitro and the nitrite structure! Therefore using a nitrite for nucleophilic
substitution on a organic compound *would* work.
I have also been thinking about preparing the nitric acid salt of oxamide.
Yesterday I attempted to prepare oxamide by heating ammonium oxalate; that procedure failed miserably. :-/ I now have black carbon fused to the bottom
of my beaker.
(COONH4)2 --> 2C + N2 + 4H2O
I am somewhat surprised that equation was dominant, rather than:
(COONH4)2 --> (CONH2)2 + 2H2O --> (CN)2 + 4H2O
I now think the below equation will happen:
(COOCH2NO2)2 + 2NH3 --> (CONH2)2*CH2NO2OH + CH2NO2OH
[Edited on 26-5-2002 by madscientist]
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PHILOU Zrealone
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Esters hydrolyse in basic and acidic conditions!
So you will never be able to make O2N-CHO-CO-CO-OCH-NO2 from HNO3/H2SO4 and an ester; you will simply make a transesterification and get the methyl
nitrate.
Better do the unstable Cl-CH2-NO2 and allow it to react with NaO2C-CO2Na in a suitable solvant for Nucleophilic substitution!
Or work with the dangerously powerful C(NO2)3-CH2OH or CH(NO2)2-CH2OH:
resulting molecule C(NO2)3-CH2-O2C-CO2-CH2-C(NO2)3 and
CH(NO2)2-CH2-O2C-CO2-CH2-CH(NO2)2
The later is the adduct of oxalic acid with gem dinitroethene; estimated power close to that of hexanitrobenzene (VOD 9,8 km/s).
PH Z
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frogfot
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I'm wondering.. Some esterification reactions with formic acid does not require any mineral acid catalyst because formic acid is enough acidic.
Now, since the first protone in oxalic acid is much more acidic than in formic acid would esterification between oxalic acid and MeOH proceed without
sulfuric acid?
Though I'm suspecting that only one Me group would be attached...
Also what about this previously discussed reaction:
(COOMe)2 + 2NH3 ==> (CONH2)2 + MeOH
Couldn't the amide be oxidised to nitro group?
(CONH2)2 =KMnO4=> (CONO2)2
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vulture
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I forgot about this! The NO2 group resonates between the nitro and the nitrite structure!
Not true. You are breaking a bond here when changing back and forth from nitrite and nitro. That's not resonance that's tautomerization.
Tautomerization happens MUCH more slowly than resonance.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
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verode
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| Quote: | Originally posted by madscientist
I believe that dinitrodimethyl oxalate would be a fairly powerful, and fairly sensitive, energetic compound. This is my planned route of preparation:
(COOH)2 + 2CH3OH --(H2SO4)--> (COOCH3)2 + 2H2O
(COOCH3)2 + 2HNO3 --(H2SO4)--> (COOCH2NO2)2 + 2H2O
It would detonate as follows:
(COOCH2NO2)2 --> N2 + 2CO + 2CO2 + 2H2O
It may be well-suited as a booster explosive for less sensitive high explosives.
[Edited on 25-5-2002 by madscientist] |
the reaction
COOCH3)2 + 2HNO3 --(H2SO4)--> (COOCH2NO2)2 + 2H2O
is impossible because the oxident power
of HNO3 towards the HCOO-COOH
strong reductor
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halogen
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nitrite <--» nitro
Hawleys condensed Chem. Dictionary states two very different entries for methyl nitrite and nitromethane. I suppose it would be the same with other
substances.
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