Sciencemadness Discussion Board

Dinitrodimethyl oxalate

madscientist - 24-5-2002 at 22:19

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]

Nick - 25-5-2002 at 04:30

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?

madscientist - 25-5-2002 at 10:54

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

madscientist - 25-5-2002 at 19:35

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.

madscientist - 25-5-2002 at 20:55

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.

Nick - 26-5-2002 at 03:46

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!

madscientist - 26-5-2002 at 06:40

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]

PHILOU Zrealone - 16-8-2002 at 08:01

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

frogfot - 28-6-2003 at 02:06

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

vulture - 28-6-2003 at 02:11

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.

verode - 11-9-2005 at 14:26

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

nitrite <--» nitro

halogen - 21-9-2005 at 13:23

Hawleys condensed Chem. Dictionary states two very different entries for methyl nitrite and nitromethane. I suppose it would be the same with other substances.