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Author: Subject: HHTDD, ENTA, DAHA
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[*] posted on 10-6-2006 at 21:57
HHTDD, ENTA, DAHA


Can anyone find dome synthesis information on these?

HHTDD-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatri-cyclo[7.3.0.0.]dodecane-5,11-dione
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[*] posted on 11-6-2006 at 07:07


Quote:
Originally posted by =SkyNET=
Can anyone find dome synthesis information on these?

HHTDD-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatri-cyclo[7.3.0.0.]dodecane-5,11-dione



J. Org. Chem. 1991,56, 3413-3419 [attached]

And more info on its DFTHP precursor here: http://www.sciencemadness.org/talk/viewthread.php?tid=6000

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[*] posted on 11-6-2006 at 15:11


Thanks.

Now just need DAHA and ENTA

ENTA

DAHA

There's also a new furazan MNOTO, but I think that needs it's own thread.

[Edited on 12-6-2006 by =SkyNET=]
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[*] posted on 12-6-2006 at 01:20


What are the properties of ENTA and DAHA?
Are they primary?




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[*] posted on 12-6-2006 at 03:31


Not sure about the diaminohexazido compound, but diaminotetrazidocyclotriphosphazene P3H4N17 is a crystalline explosive, where hexaazidocyclotriphosphazene P3N21 is a liquid primary. Formed from NaN3 on the corresponding chlorides.

Hexachlorocyclotriphosphazene is made by condensing PCl5 with ammonia, but I've never seen the conditions needed in literature. Nor have I seen conditions for a cyclotetraphosphazene ring though a lot of higher and lower analogues are known. Further reaction with aqueous ammonia yields the diamino compounds.

Dont quote me but ENTA was investigated as a "green" crystalline primary but failed, due to inability to DDT if I remember correctly. Never seen how its made though. I guess instead of ammonia condensing EDNA or ethylenediamine then nitration.

[Edited on 12-6-2006 by Axt]
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[*] posted on 12-6-2006 at 05:55


Searching for its name at the patent office is always a good start.

"The present invention relates to a novel cyclotetraphosphazene compound and a method of producing the same. In particular, the present invention relates to 1,1-diamino-3,3,5,5,7,7 hexaazidocyclotetraphosphazene, which has shown to be useful as an energetic composition and a percussion primer .... etc." US6232479

The patent also referes to and gives reference for the ethylenedinitramine derivative ENTA:

"Cyclotriphosphazenes have been reported as energetic compounds in Novel Spiro Substituted Cyclotriphosphazenes Incorporating Ethylenedinitramine Units, Dave, et al., Phosphorus, Sulfur, and Silicon, 1994, vol. 90, pp. 175-184"

There is also a liquid isomer "1,5-diamino-1,3,3,5,7,7-hexaazidocyclotetraphosphazene" as described in patent #US6218554.

[Edited on 12-6-2006 by Axt]

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[*] posted on 12-6-2006 at 06:10


This is the not very detailed synthesis of diaminotetraazidocyclotriphosphazene.

SYNTHESIS OF TRIPHOSPHONITRILIC DIAMIDETETRAAZIDE
M. S. Chang, A. J. Matuszko
J. Am. Chem. Soc.; 1960; 82(21); 5756-5757 [attached]

Can I recommend this thread be chopped apart and renamed "Energetic Cyclophosphazenes" or words to that effect. This is what happens when people request spoonfeeding on unrelated general topics in a single thread... It looks like shit, dont it skynet?

[Edited on 12-6-2006 by Axt]

[Edited on 12-6-2006 by Axt]

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[*] posted on 12-6-2006 at 10:13


Found something on phospahazenes.

http://202.41.85.161/~kcks/icc2003.pdf

there's some more phosphorus related articles here, figured someone could use it.

http://202.41.85.161/~kcks/publications.htm

[Edited on 12-6-2006 by =SkyNET=]
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[*] posted on 12-6-2006 at 20:59


The synthesis by Liebig of hexachlorocyclotriphosphazene from phosphorus pentachloride and ammonia or ammonium chloride is of historical interest (206), and modifications included the use of sealed tubes (351, 352, 353) or use of an inert solvent such as sym-tetrachloroethane (246, 308). Other preparative methods include the reaction of ammono-basic mercuric chloride with phosphorus pentachloride (136, 317, 138), the high temperature chlorination of phosphorus nitrides (232, 234, 239, 378), and reaction between tetrasulfur tetranitride, thionyl chloride, and phosphorus trichloride (143).

(206) Liebig, J., Ann., 11, 139 (1834).
(351) Stokes, H. N., Am. Chem. J., 17, 275 (1895).
(352) Stokes, H. N., Ber., 28, 437 (1895).
(353) Stokes, H. N., Am. Chem. J., 18, 629 (1896).
(246) Nielsen, M. L., and Cranford, G., Inorg. Syntheses, 6, 94 (1960).
(308) Schenk, R., and Romer, G., Ber., 57B, 1343 (1924).
(136) Gladstone, J. H., and Holmes, J. D., J . Chem. Soc., 17, 225 (1864)
(317) Scott, E. S., and Audrieth, L. F., J. Chem. Ed., 31, 168 (1954).
(138) Gladstone, J. H., and Holmes, J. D., Bull. soc. chim., 3, 113 (1865).
(232) hloureu, H., Rosen, B., and Wetroff, G., Compt. rend., 209, 207 (1939).
(234) Moureu, H., and Wetroff, G., Compt. rend., 204, 51 (1937).
(239) Moureu, H., and Wetroff, G., Compt. rend., 210, 436 (1940)
(378) Wetroff, G., Compt. rend., 208, 580 (1939).
(143) Goehring, M., and Heinke, J., Z. anorg. Chem., 278, 53 (1955)

The Phosphonitrilic Chlorides and their Derivatives
Chem. Rev.; 1943; 32(1); 109-133.
http://rapidshare.de/files/22923936/the_phosphonitrilic_chlo...

The Phosphazenes (Phosphonitrilic Compounds)
Chem. Rev.; 1962; 62(3); 247-281.
http://rapidshare.de/files/22925672/the_phosphazenes.pdf.htm...

Recent advances in phosphazene (phosphonitrilic) chemistry
Chem. Rev.; 1972; 72(4); 315-356.
http://rapidshare.de/files/22925174/recent_advances_in_phosp...
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[*] posted on 7-4-2009 at 18:32


Synthesis of cis-syn-cis-2,6-Dioxo-1,3,4,5,7,8-hexanitrodecahydro-lH,5H-diimidazo[4,5-b:4',5'-e]pyrazine (HHTDD)



White crystalline plates, melts ~210C (explosive decomposition). Crystal density is 2.07 g/cm3 and is greatest among CHNO explosives made so far. Heat of explosion is 5.81 MJ/kg, detonation pressure is 46.1 GPa, throwing ability is 118% of HMX (HNIW – 108%). Sensitive to impact and friction, impact sensitivity is 21 cm with 2.5 kg weight (HMX – 26 cm). Detonation velocity is 9019 m/sec at 1.862 g/cm3, 9546 m/sec at 1.995 g/cm3 and 9800 m/sec at 2.07 g/cm3 (TMD). Soluble in acetone and benzene, insoluble in water.


Procedure from: J. Org. Chem. 1991, 56, 3413-3419.



1. l,4-Diformyl-2,3,5,6-tetrahydroxypiperazine. Formamide (135 g, 119 ml, 3.0 mol) was added to stirred aqueous glyoxal (40% w/w, 435 g, 3.0 mol), and the pH was adjusted to 8.5 by using aqueous sodium hydroxide solution (10 M). The temperature rose slowly to 30°C over the first 30 min, and the solution developed a yellow tinge. The exotherm subsided, and after 4 h of stirring, the mixture was left to stand for 3 days. A first crop of the product (93 g) was collected by filtration, and a second crop was obtained by adjusting the pH of the filtrate to 9, the temperature of the mixture being controlled at 25°C with ice/water and the additional product being collected after 5 h. Both crops were washed well with water, dried, and purified by digesting the solid twice in a hot mixture of dimethylformamide/water (80:20). This involved using 70 ml of this mixture for each 30 g of solid, maintaining the stirred slurry at 75°C for 30 min, then cooling it to 30°C, collecting the solid, and washing it well with water. The product was dried over a desiccant to give a white solid (204 g, 66%), which darkened substantially above 190 °C and decomposed above 210°C (lit. mp ca. 225°C dec).




2. cis-syn-cis-2,6-Dioxodecahydro-lH,5H-diimidazo[4,5-b:4',5'-e]pyrazine. Finely ground l,4-diformyl-2,3,5,6-tetrahydroxypiperazine (24 g, 0.115 mol) was added to a stirred solution of urea (21 g, 0.35 mol) in concentrated hydrochloric acid (37% w/w, 100 ml) over 15 min. The mixture was stirred for 90 h, after which time the HNMR spectrum of a sample showed that all starting material had been consumed (#1). The solid was collected by filtration, washed with methanol (300 ml), and dried at aspirator vacuum and then at 75°C (1 mm) to give the crude product (28.2 g, 80.2%) as a hydrate of the dihydrochloride salt. This was dissolved in chilled water (22.5 ml/g) and precipitated by the addition of cold methanol (100 ml/g) to give the mono-hydrochloride salt (10.3 g, 38%), which darkens above 170°C: mp 183-185°C dec. (corrected). Alternatively, the crude salt may be converted to the mono-hydrochloride by precipitation from an aqueous solution (1 g/10 ml) by the addition of acetone (3 ml/ml of solution); the yield was 32% based on piperazine starting material.




3. cis-syn-cis-2,6-Dioxo-1,3,4,5,7,8-hexanitrodecahydro-lH,5H-diimidazo[4,5-b:4',5'-e]pyrazine. Phosphorus pentoxide (15.6 g, 10.0 mmol) was slowly added to absolute (100%) nitric acid (30 ml, 750 mmol) which was stirred under nitrogen and cooled in ice/water to keep the temperature of the acid below 30°C. The mixture was then maintained at 30°С for 40 min to give a clear yellow solution. The stirred solution was cooled to -15°C and kept below -10°C as the monohydrochloride salt (1.2 g, 0.5 mmol) was added in portions over 30 min (#2). The mixture was allowed to warm to 25°C over 1.5 h and was maintained at this temperature for 30 min, then at 35°C for 1 h, and at 45°C for 2h. The cooled mixture was stirred into ice/water (300 ml). The precipitated solid was quickly collected by filtration (#3), washed with cold water and dichloromethane, and then dried to give the crude product (1.78 g, 74%): mp 210°C explosive dec.


Notes:

1. It is essential that stirring must be continued during all aging period, because without stirring condensation reaction slows down greatly, and after aging period only traces of reaction product are formed. During aging process mixture becomes more and more viscous, so strong mechanical stirring is advised. Insolubility of source product l,4-Diformyl-2,3,5,6-tetrahydroxypiperazine allows to control reaction state, by measuring amount of water-insoluble material in sample taken from reaction flask. At the end of aging period mixture must have visible pink coloration, and sample of reaction product should easily dissolve in water, leaving no insoluble residue.


2. Addition of phosphorus pentoxide to 99% nitric acid is very exothermic, and effort must be taken to keep mixture temperature below 30C during all addition period, to minimize thermal decomposition of forming nitrogen pentoxide. This can be achieved by cooling acid in ice bath and adding phosphorus pentoxide in small portions, allowing exotherm to subside before adding new several portions. Addition of monohydrochloride salt is also exothermic, but in this case temperature must be maintained below -10C during course of addition, because higher temperature can lead to uncontrollable oxidation processes. It is convenient to use ice/table salt bath for cooling during this period, bath has cryoscopic point at -21.3°C, and can be prepared by mixing 33g of sodium chloride per 100g of finely crushed ice, placing it by thin layers at the top of each other.


3. Reaction product is readily hydrolyzed by water, hydrolysis goes with visible speed even at 30C, so contact time with warm water should be minimized to prevent loses of reaction product. Pouring acid mixture to ice/water should be accompanied by intense stirring, to prevent local overheat, and precipitated product must be filtered and dried with organic solvent as fast as possible. Dichloromethane washing can be substituted by washing with small amount of isopropyl alcohol and placing product to desiccator.


Pictures:



Condensation of glyoxal with formamide in basic environment proceeds smoothly, soon after beginning of aging product begins to precipitate as layer of snow white solid. Then reaction is complete it is filtered, dried, weighted and purified. Right photo shows pure l,4-Diformyl-2,3,5,6-tetrahydroxypiperazine.




Condensation of 1,4-Diformyl-2,3,5,6-tetrahydroxypiperazine with urea in hydrochloric acid, proceeds harder and require constant stirring. Then mixture is left unstirred during aging, only traces of condensation product are formed. During aging mixture becomes more and more viscous, so mechanical stirring is advised. Then reaction is close to completion mixture became pinkish, and sample of solid taken from reaction mixture easily dissolves in water, leaving no insoluble residue. Photo on the right show crude piperazine/urea condensation product.




Mother liquor obtained after filtering has intense red coloration, substance causing it is unknown. Crude product is purified by dissolving in water (middle photo) and reprecipitated by addition of acetone, forming snow-white flakes of pure monohydrochloride salt, shown on right photo.




Nitration of monohydrochloride to HHTDD takes place only by action of N2O5 solution in anhydrous nitric acid, such solution has characteristic yellow color, show on left photo. Solution of nitrogen pentoxide is cooled to ~ -20C, and monohydrochloride is added in small portions with rate, not allowing temperature to rise above -10C. Then all monohydrochloride is added solution is allowed to warm to room temperature in 1.5 hours, and deep nitration is forced by further heating as described in synthesis procedure. For relatively low temperature baths, it is convenient to use running hot water stream from water supply system, eventually checking out water temperature on thermometer.




Then reaction mixture is heated to 45C substantial amount of nitrogen dioxide and nitric acid fumes are evolved, these are allowed to escape from reaction flask through the small hole in flask cap. Left photo shows reaction mixture after 2 hours at 45C, photo on the right shows HHTDD, obtained by pouring acid mixture on ice/water and quick filtering.


[Edited on 8-4-2009 by Engager]




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[*] posted on 8-4-2009 at 04:09


Excellent job Engager,

I remember that what causes the unstability of that HHTDD molecule are the two distorded pentarings at each edges of the molecule...it is also what renders the cyclisation so difficult because the initial 1,4-Diformyl-2,3,5,6-tetrahydroxypiperazine has its vicinal OH part of the time axial to each other, and part of the time equatorial to each other vs the piperazine hexaring in chair conformation...this must account for the long reaction time between urea and the piperazine.

One might also consider the possibility of the central hexaring to be in the boat conformation and so two pentarings would condensate after each other in a stressless fashion, the overal molecule would then be bended in a near caged structure a bit like the TEX molecule in Axt's tread.

Also avoiding the H atoms in the molecule, thus bringing some kind of aromaticity ( see DHHTDD- Dehydrogeno-HexanitroHexaazaTricycloDodecaneDione drawing in attachement aside HHTDD) would not only:
1°)exclude the stress in the molecule, rendering it stabler towards shock/friction than HHTDD
2°)increase the energy per volume/weight and thus the energy output... multiple bonds store energy
3°)increase the density by making a nearly aromatic planar molecule, much planar than the original drawing
4°)Closer to zero Oxygen Balance
5°)Exclude Hydrogen from the original molecule and so increase the heat output, H2O generation in detonation process tempers somehow the detonation heat owing to its high heat capacity.

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[Edited on 8-4-2009 by PHILOU Zrealone]




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[*] posted on 8-4-2009 at 11:18


Coincidentally, I'm working on synthesizing HHTDD at this very moment, although I'm using potassium sulfaminate instead of formamide (initial results seem to indicate that the condensation of the tetrahydroxypiperazine disulfonate with urea doesn't give as high a yield as that reported for the diformylpiperazine).
In the article that Engager is working from, they show the structure that they have established by X-ray crystallography, and as Philou said, it is very very close to TEX (or HNIW). So, I'm going to try to hydrolyse HHTDD to remove the two carbonyls, and then condense the product with glyoxal, producing either HNIW or HNW.
This approach is described very briefly in this SERDP report (pages 10-11):

http://www.serdp.org/Research/upload/WP-1518-FR.pdf

and it seems that they had some success conducting the hydrolysis in nitromethane/sulfuric acid with excess trimeric glyoxal. At that point in the report, they abandon that route in favour of an allylamine analog to HBIW, so there aren't really any experimental details.
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[*] posted on 8-4-2009 at 17:29


Very well done Engager

Excellent post.

In your first (1) reaction schematic diagram (the reaction with Glyoxal) I noticed you named the Formamide molecule “Urea”. A typing error I’m sure.

By the way (just for interest sake) : What would the reaction product (1) be if one uses Urea in stead of Formamide?

Step 3 : You are using 99% Nitric acid. What will happen when one uses Nitric acid of a slightly lower concentration, i.e. 95% or so? Is the reaction (or yield) compromised by doing so? Might the adding of 98% Sulfuric acid, to lets say 95% Nitric acid (before adding the Phos. Pentoxide) perhaps help to compensate for (absorb) the 5% water (in the Nitric acid)? Or should Sulfuric acid rather be avoided totally (when working with Phos. Pentoxide in HNO3) ?

Unfortunately, the poor hydrolytic stability of HHTDD limits its value as a practical explosive.

>>>
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[*] posted on 11-4-2009 at 00:39


Quote: Originally posted by Plasmapyrobattics  
Very well done Engager

Excellent post.

In your first (1) reaction schematic diagram (the reaction with Glyoxal) I noticed you named the Formamide molecule “Urea”. A typing error I’m sure.

By the way (just for interest sake) : What would the reaction product (1) be if one uses Urea in stead of Formamide?

Step 3 : You are using 99% Nitric acid. What will happen when one uses Nitric acid of a slightly lower concentration, i.e. 95% or so? Is the reaction (or yield) compromised by doing so? Might the adding of 98% Sulfuric acid, to lets say 95% Nitric acid (before adding the Phos. Pentoxide) perhaps help to compensate for (absorb) the 5% water (in the Nitric acid)? Or should Sulfuric acid rather be avoided totally (when working with Phos. Pentoxide in HNO3) ?
>>>


Actualy "urea" in first reaction this is an typing error, but if you use urea instead of formamide for condensation with glyoxal you will end up in glycouryl (TNGU-SORGYUL base cage). Now about acid - actualy yield will suffer if you use weaker acid, because any molecule of water present will react with N2O5 witch is essential to full nitration, decreasing mixture nitrating activity. Strong HNO3/H2SO4 mixtures can afford placing only four nitro groups. To use weaker nitric acid, you need first to dehydrate in with calculated ammound of P2O5 and destill it, howerver using lower then 99% nitric acid and adding P2O5 in amount corresponding summ of amount mentioned in procedure plus amount required for dehydration of HNO3 may work just fine.


[Edited on 11-4-2009 by Engager]




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