Sciencemadness Discussion Board - 1,1,3,5,5-pentanitro-1,5- di-(5-nitrotetrazolato-N2)-3-azapentane

1,1,3,5,5-pentanitro-1,5- di-(5-nitrotetrazolato-N2)-3-azapentane

Lotilko - 1-1-2017 at 12:30

Hey folks.
I stubled across a nice article a few months ago written by Engager:

http://www.sciencemadness.org/talk/viewthread.php?tid=11850

The document features 2 compounds interesting as high performance explosives on page 27. I am mainly interested in the second, 1,1,3,5,5-pentanitro-1,5- di-(5-nitrotetrazolato-N2)-3-azapentane. It has a rather high density and estimated detonation velocity compared to other high explosives. I checked the cited references without luck. I tried google, but I found nothing about said substance.

Dany made a thread about energetic salts with similar structures:

http://www.sciencemadness.org/talk/viewthread.php?tid=25650

Most of the salts posess very good energetic properties despite the poor thermal stabilities. The starting material is BDNENA which is easily synthesized from common chemicals. Although Engager mentions it's synthesis, I think 1,1,3,5,5-pentanitro-1,5- di-(5-nitrotetrazolato-N2)-3-azapentane could be prepared from BDNENA via chlorination and reaction with sodium nitrotetrazolate. Any thoughts?

I would need information about it's sensitivity, energetic and physical properties. Thanks in advance.

Dornier 335A - 2-1-2017 at 03:04

I've attached the only reference I have found. Don't get too excited though, it's in Chinese.

Engager's Russian references seem impossible to find on the internet.

Attachment: 1,1,3,5,5-pentanitro-1,5-bis(5-nitrotetrazol-2-yl)-3-azapentane.pdf (685kB)
This file has been downloaded 663 times

PHILOU Zrealone - 2-1-2017 at 03:18

For those who like it more in extension or chemically written:
PNDNTAP is 1,1,3,5,5-pentanitro-1,5- di-(5-nitrotetrazolato-N2)-3-azapentane
or O2N-CN4-C(NO2)2-CH2-N(NO2)-CH2-C(NO2)2-N4C-NO2 --> a perfect OB High Explosive.
BDNENA is bis-(2,2-dinitroethyl)nitramine
or (O2N)2CH-CH2-N(NO2)-CH2-CH(NO2)2

So both share the same core and the two acidic protons of the dinitromethyl extremities of BDNENA have been replaced by nitrotetrazoles into PNDNTAP.

Into Engager paper the PNDNTAP is indeed made by:
1°) halogenation: the acidic protons of the dinitromethyl extremities of BDNENA are easily replaced by halogens in basic media...just like chloropicrin (trichloronitromethane) from nitromethane.
2°) methatesis from silver nitrotetrazolate and the reactive halogen compound: alfa-halo-nitro or -dinitro compounds are quite reactive hence the toxicity of chloropicrine as war-gas/-liquid...with as driving force the precipitation of silver halide.

Maybe substituting silver nitrotetrazole by sodium salt may give something under specific tuned conditions (solvent, temperature, ...).

Lotilko - 2-1-2017 at 03:40

The attached file does not seem to work, although thanks for the insight.

There are only a few explosives which exhibit detonation velocities above 10 km/s, although PNDNTAP indeed has a high density, I am skeptical about 10600 m/s. If it's actually that high, it should posess unmatched brisance. Is that right? Also could the low 65 C melting point mean poor thermal stability?

PHILOU Zrealone - 2-1-2017 at 04:15

Quote: Originally posted by Lotilko

The attached file does not seem to work, although thanks for the insight.

There are only a few explosives which exhibit detonation velocities above 10 km/s, although PNDNTAP indeed has a high density, I am skeptical about 10600 m/s. If it's actually that high, it should posess unmatched brisance. Is that right? Also could the low 65 C melting point mean poor thermal stability?

The attached file worked fine for me although mostly into chinese or japanese.

Low MP doesn't mean poor thermal stability...it only means poor molecular cohesion, less molecular attracting forces, H-bonds.
It is strange that such a dense large molecule has such a low MP.

Other interesting target molecules would be polymeric:
1°) (-C(NO2)2-CH2-N(NO2)-CH2-C(NO2)2-)n
A perfect OB linear polymer...predicted density will be high (over 2.1 g/cm³) and of low sensitivity owing to its polymeric nature.
2°) (-C(NO2)2-CH2-N(NO2)-CH2-C(NO2)2-CH2-)n
Almost perfect OB polymer, if the C(NO2)2 doesn't like to be neightbourgs, a little CH2 spacing providing more stability and a little hydrogen and a little negative OB.
3°) (-C(NO2)2-CH2-N(NO2)-CH2-)n
Another almost perfect OB polymer...the cyclic dimer reminding of HMX has been synthesized and is quite powerful but less efficient than HMX.

A retrosynthetic approach gives the feeling they may be done by varying the proportions of 3 reactants: CH2=O, CH2(NO2)2 and H2N-NO2; sadly the last two are not very stable.

[Edited on 2-1-2017 by PHILOU Zrealone]

Dornier 335A - 2-1-2017 at 05:09

PHILOU Zrealone, you must have confused PNDNTAP with 1,3-bis(5-nitrotetrazolato-N2)-2-nitro-2-azapropane. That one is indeed made using metathesis from silver nitrotetrazolate. In engager's paper (and the Chinese one) PNDNTAP is synthesised something like this:

The BDNENA route seems much easier though if it gives reasonable yield.

PHILOU Zrealone - 2-1-2017 at 05:21

Quote: Originally posted by Dornier 335A

PHILOU Zrealone, you must have confused PNDNTAP with 1,3-bis(5-nitrotetrazolato-N2)-2-nitro-2-azapropane. That one is indeed made using metathesis from silver nitrotetrazolate. In engager's paper (and the Chinese one) PNDNTAP is synthesised something like this:

The BDNENA route seems much easier though if it gives reasonable yield.

Yes, thank you for pointing this out, you are right, I mixed up the two synthesis that were into the same paragraph.

Anyway the metathetic process of silver nitrotetrazolate and dichloro-BDNENA seems also a plausible way to get to PNDNTAP...but maybe the driving force (precipiting silver halide) must be enhanced if it doesn't suceed with the dichloride by passing from dichloro- to dibromo- or even to diiodo-BDNENA.

The chinese/engager process may be improved by using one quivalent of H2N-NO2 and 2 CH2=O (or 1 equiv HOCH2-N(NO2)-CH2-OH) with two of nitrotetrazolyl-dinitromethane...to spare the last nitric-sulfuric acid nitration step.

[Edited on 2-1-2017 by PHILOU Zrealone]

Lotilko - 2-1-2017 at 05:29

Well, I have a few files on BDNENA and related compounds. I'll look into it and see if it would be feasible.

I really want to take a look at the pdf. Dornier, could you please provide a link to it. All I can see is this:

Maybe because I am on a phone?

[Edited on 2017.1.2 by Lotilko]

PHILOU Zrealone - 2-1-2017 at 07:02

Quote: Originally posted by Lotilko

Well, I have a few files on BDNENA and related compounds. I'll look into it and see if it would be feasible.

I really want to take a look at the pdf. Dornier, could you please provide a link to it. All I can see is this:

Maybe because I am on a phone?

[Edited on 2017.1.2 by Lotilko]

There is indeed that filter above and accros the text.

Maybe your reader doesn't like chinese/japanese symbols.