Sciencemadness Discussion Board

reduction of syphnic acid

blindreeper - 1-3-2003 at 00:04

I was doing some thinking. Picric acid (trinitrophenol) and styphnic acid (trinitoresocinol) are very similar. Picric acid is reduced to picramic acid with sodium sulfide. This in turn is made into DDNP.

I lack the great knowledge of organic chemistry, but could styphnic acid be reduced to something similar to picramic acid but with an extra OH and then made into a DDNP type substance (diazodinitroresorcinol)?

I think this is all crazy talk from a childish mind but you never know it could work.
Any comments?

If anyone has some syphnic acid/resorcinol and alot of time maybe they could try this.

Also if this is not new and been dicussed before please excuse me.

fluffy bunny - 1-3-2003 at 01:34

Yes that is certainly possible! Theoretically, any aromatic-amine can be diazotised.
However, there could be certain difficulties that would make it impossible to make, and i don't mean to sound negative, but if it were a useful primary, it probably would have been documented already.
But i certainly think it would b an interesting experiment, with caution.

KABOOOM(pyrojustforfun) - 11-3-2003 at 20:42

the next case after s<b>t</b>yphnic acid is trinitrophloroglucinol. <a href="http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO1&Sect2=HITOFF&d=PALL&p=1&u=/netahtml/srchnum.htm&r=1&f=G&l= 50&s1=4,434,304.WKU.&OS=PN/4,434,304&RS=PN/4,434,304">Patent US4434304</a> is <i>Synthesis of trinitrophloroglucinol</i>.

Madog - 12-3-2003 at 11:45

yeah, i bet it would be good but the sensitiveity might be bad. i had the same idea a little while ago

PHILOU Zrealone - 24-3-2003 at 03:55

Styphnic acid: C6H(OH)2(NO2)3
OB: -35,9%
Volume of detonation gases: 680L/kg
density: 1,83g/ccm
lead block test: 284 ccm/10g
impact sensitivity: 7,4 Nm
heat of explosion (H2O l): 4271 kJ/kg
VOD :?

Picric acid: C6H2(OH)(NO2)3
OB: -45,4%
VODG: 800L/kg
density: 1,767g/ccm
LBT: 315 ccm/10g
IS: 7,4 Nm
heat of explosion (H2O l): 4522 kJ/kg
VOD : 7350 m/s @ 1,7g/ccm and confined

Picramic acid: H2N-C6H2(OH)(NO2)2
OB: -76,3%
VODG: 800L/kg
density: ?
LBT: 166 ccm/10g
IS: 34 Nm
Heat of explosion (H2O l): 2722 kJ/kg
VOD: ?

DDNP: C6H2(-O-)(-N=N-)(NO2)2
OB: -60,9%
VODG: ?
density: 1,63g/ccm
LBT: 326 ccm/10g
IS: 1,5 Nm
HOE : ?
VOD: 6600 m/s confined @ 1,5g/ccm

1)From the above datas, you can conclude that styphnic acid has a better density and a better OB than picric does; but since it contains more H will produce more H2O what will reduce its heat of explosion!
Anyway in the salts of those acids there will be less H and here you may conclude that the heavy salts of those will be stronger primaries than the ones of TNP!
TNPhloroglucidates > Styphnates > picrates in VOD, density, heat output, OB, brisance!
Sensitivity is the same for the pure acids and TNPG should also be close!

2)The transformation of TNP into PAA lowers the density and the OB but reacting PAA to DDNP yields an explosive of better LBT and similar VOD but with lower OB and much higher sensitivity than the original TNP!

3)The formation of DDNP brother of styphnic acid and TNPG will lead to free acid -OH groups that will be able to make salts!
The free acid will already be much more sensitive than TNP and their salts must be even more sensitive!
(HO)C6H(-O-)(-N2-)(NO2)2 looks like TNP
(HO)2C6(-O-)(-N2-)(NO2)2 looks like TNR

With stronger reductors one might have:
didiazonitroresorcinol C6H(O)2(N2)2(NO2)
didiazonitrophloroglucidol HO-C6(O)2(N2)2(NO2)
tridiazophloroglucidol C6(O)3(N2)3

Which should have initiating habilities but maybe are too sensitive!!!

:cool::o:cool::o:cool:

PHILOU Zrealone - 24-3-2003 at 04:01

Also something that would be much more interesting would be to nitrate picramic acid (maybe after protection of the NH2 by acylation) with conc HNO3 and H2SO4 to get 3,4,5,6 tetranitro-2 aminophenol (moderate sensitive very HE)
The later can also make a DTeNP primary of much higher energy output!
C6(O)(N2)(NO2)4
:cool:

KABOOOM(pyrojustforfun) - 27-3-2003 at 17:39

knowing the fact that aromates having -NH2 and -OH in para position also form diazooxides, we can predict more explosive compounds.
for instance diazotation of nitration product of para-aminophenol(made by hydrolyzation of acetaminophen tablets) sounds interesting. all u have to do is to add the tablets in a dilute acid solution, cool it down, collect the crystals, add the crystals to mixed acid, diazotiate the product to get brother of DDNP. it is easier to make than DDNP, as there's no reduction step.
acetaminophen is very easy to purchase (cheap too)

franklyn - 16-3-2010 at 16:05

An Improved Preparation of Trinitrophloroglucinol
A. A. Defusco; A. T. Nielsen; R. L. Atkins
Organic Preparations and Procedures International: The New Journal for Organic Synthesis,
Volume 14, Issue 6, (1982) Pages 393 – 395
This is the patent posted above _
Synthesis of Trinitrophloroglucinol US4434304


Studies on 2,4,6-trinitrophloroglucinol (TNPG) A novel flash sensitizer
Mehilal, N Sikder, A K Sikder, D V Survase & J P Agrawal
Indian Journal of Engineering & Materials Sciences , Vol. 11, February 2004, pp. 59-62

2,4,6-Trinitrophloroglucinol (TNPG), useful for percussion caps, detonator
formulations and dye manufacture, has been synthesized with conventional
nitrating agents under mild reaction conditions. The compound is characterized
by IR, NMR, mass and elemental analyses. Further, the purity of the compound
is confirmed by estimation of nitro groups. Thermal and explosive properties of
TNPG have been investigated. The detonation velocity and detonation pressure
are also estimated.

http://chemicalland21.com/lifescience/phar/1,3,5-TRIHDROXY%2...

The major shortcoming to the syntheses of trinitrophloroglucinol is that
phloroglucinol is about $50 a pound in bulk quantity. Trinitrophloroglucinol
and triaminotrinitrobenzene synthesis from inexpensive nitroarenes such
as picric acid are detailed in the following patents _

Synthesis and Purification of 1,3,5-Triamino-2,4,6-Trinitrobenzene (TATB)
This is the patent _ US 7057072

Synthesis of Trinitrophloroglucinol and Triaminotrinitrobenzene (TATB)
This is the patent _ US 7057073


Related threads _
http://www.sciencemadness.org/talk/viewthread.php?tid=5406
http://www.sciencemadness.org/talk/viewthread.php?tid=4457

.

Trinitro phloroglucinol.gif - 25kB

PHILOU Zrealone - 17-3-2010 at 05:09

Hi Franklyn,
I'm interested...you wrote:
"Thermal and explosive properties of
TNPG have been investigated. The detonation velocity and detonation pressure
are also estimated."

Can you write those data down?
The link under only goes to 1,3,5-trihydroxybenzene and related compounds...TNPG lead salt CAS number is wel listed but not the datas :( (CAS 51325-28-1)

Thank you.

PHZ

franklyn - 18-3-2010 at 23:26

Quote: Originally posted by PHILOU Zrealone  

I'm interested...you wrote:
"Thermal and explosive properties of TNPG have been investigated.
The detonation velocity and detonation pressure are also estimated."

PHILOU Zrealone
I don't have the article , It's just the abstract shown here _
http://www.niscair.res.in/ScienceCommunication/ResearchJourn...
Unfortunately the free access journals don't include those from Vol 11 , 2004
http://nopr.niscair.res.in/handle/123456789/36

The only source I could find is this _ http://cat.inist.fr/?aModele=afficheN&cpsidt=15541560

A related paper is available from here _ http://dx.doi.org/10.1016/j.jhazmat.2007.01.043

these are best requested in the references section.

.

quicksilver - 19-3-2010 at 15:46

This was the materia (2,4,6-Trinitrophloroglucinol)l that originally put me off Legard (Preparatory Manual of explosives). Not only could I not find ONE of his sited patents (this was the 2nd edition I think) but the synthesis was exceedingly wasteful of acid.

Peroxid - 22-3-2010 at 10:36

Hi!

Here is this (http://dx.doi.org/10.1016/j.jhazmat.2007.01.043 ) reference about TNPG.

Attachment: TNPG2.pdf (200kB)
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