Far more powerful than Astrolite

Quote: Originally posted by gregxy

The chemistry of explosives has been well understood for decades. Furthermore the universities and big labs have had enormous resources to throw at the problem. So most everything that is usefull has aleady been patented and/or put to use. Here "usefull" cosiders many factors, power, stability cost etc. For each of those compounds that have been put to use, many others have been evaluated and forgotten. A home experimenter may develop something that is interesting and "useful" in the context of home experimentation, ie can be made using available materials but its almost impossible to invent something better than what is allready in use.

I have a whole thick binder full of ideas, both easy ways to make extreme starting chemicals, and new molecular structures.

The compounds in the above post might look highly unstable and sensitive, but notice the delocalized electrons. Just as perchlorate and nitroformate are stable because an extra electron resonates on the oxygen atoms, so to would that whole compound.



[Edited on 20-6-2010 by Anders Hoveland]

Quote: Originally posted by 497

Quote: "Formaldoxime" CH2NOH probably does not exist. CH2O reacts very differently from acetone. Formaldoxime would probably be the trimer, an RDX with OH instead of NO2 groups. Yes you're right it may exist as a trimer.. or a monomer but, trimer or monomer, my point is the same: you can't methylate hydroxylamine with formaldehyde... Although it may raise some interesting possibilities of using formaldoxime trimer to make some other energetics..

Quote: Originally posted by 497

I'm pretty sure you'll be wasting your time. The formaldoxime formed will immediately be tied up in it's trimer form and not react further. Or if you can somehow make/acquire N,N-dimethylcyclohexylmethylamine you could do it via this route. Good luck.. [Edited on 9-7-2010 by 497]

Another thought
HOCH2CH=O <--> O=CHCH2OH

2-hydroxyl ethyl aldehyde should condense with hydroxylamine to form
O=N--CH2CH2--N(OH)--CH2CH2--N=O

There are two optional routes from here. It can be oxidized with H2O2 to HON(CH2CH2NO2)2, or NO2 can be bubbled in to make HON(CH2C[NO2]3) through the oxime tautomer. Let me again remind of the potential for powerful, but highly stable energetic salts with the first of these compounds.

The above is somewhat speculation. Although H2O2 will apparently oxidize trimethylamine, I think dimethyl hydroxylamine would be more resistant.

I am going to include the procedure in the link above, just in case it becomes unavailable in the future. The picture is included.
In a carefully cleaned 500-ml. Erlenmeyer flask, covered with a watch glass, are placed 49.4 g. (0.35 mole) of N,N-dimethylcyclohexylmethylamine , 39.5 g. (0.35 mole) of 30% hydrogen peroxide, and 45 ml. of methanol. The homogeneous solution is allowed to stand at room temperature for 36 hours. After 2 and 5 hours hydrogen peroxide (39.5-g. portions each time) is added, The excess hydrogen peroxide is destroyed by stirring the mixture with a small amount of platinum black (Note 4) until the evolution of oxygen ceases. The solution is filtered into a 500-ml. round-bottomed flask and concentrated at a bath temperature of 50–60°, a water aspirator being used initially and an oil pump finally, until the amine oxide hydrate solidifies. A Teflon-covered stirring bar is introduced into the flask, which is then connected by a 20-cm. column to a trap (reversed to avoid plugging) cooled in Dry Ice-acetone. The flask is heated in an oil bath to 90–100°, and the apparatus is evacuated to a pressure of ca. 10 mm. with stirring of the liquefied amine oxide hydrate. When the content of the flask resolidifies, the temperature of the oil bath is raised to 160°. The amine oxide decomposes completely within about 2 hours at this temperature. Water (100 ml.) is added to the contents of the trap. The olefin layer is removed with a pipette and washed with two 5-ml. portions of water, two 5-ml. portions of ice-cold 10% hydrochloric acid and one 5-ml. portion of 5% sodium bicarbonate solution. The olefin is cooled in a Dry Ice-acetone bath and filtered through glass wool (Note 8). Distillation over a small piece of sodium through a semimicro column2 yields 26.6–29.6 g. (79–88%) of methylenecyclohexane, b.p. 100–102°
The aqueous layer is combined with the two neutral aqueous extracts and acidified by addition of 45 ml. of concentrated hydrochloric acid. The solution is concentrated under reduced pressure at 60–70° until no more distillate comes over. The residue, which solidifies on cooling, is dried in a vacuum desiccator over potassium hydroxide pellets to yield 30.7–32.7 g. (90–96%) of crude N,N-dimethylhydroxylamine hydrochloride, m.p. 103–106° (sealed tube). Crystallization from 40 ml. of isopropyl alcohol gives 26.6–30.7 g. (78–90%) of the pure hydrochloride, m.p. 106–108°

HOCH2CH=O might be possible from H2O2 and acetylene

I'm a little confused about your proposed mechanism here. I assume you mean the hydroxyacetaldehyde will form an oxime, which will then tautomerize to nitrosoacetaldehyde, react with more hydroxylamine to make nitrosoacetaldoxime, which then condenses with another nitrosoacetaldehyde to make your final di(2-nitrosoethyl)hydroxylamine?

I'm not sure if it would go like that though, for one thing, there is literature that says that the nitroso group may stabilize the enol form enough for it to be the more stable than the keto form. This might prevent it from reacting with further hydroxylamine, I'm not sure.

Also, as with synthesis of dimethyhydroxylamine, I don't think an aldehyde can N-alkylate an oxime, which is what you're saying should happen right? Do you have a mechanism for this? From what I've seen that scheme can only take place if the oxime is first hydrogenated to a monoalkyl hydroxylamine, which will react with a further amount of aldehyde.. and then that must be hydrogenated again to get the final dialkyl hydroxylamine. Not quite so easy..

Further casting doubt on your hypothesis, I found a patent where in one example they synthesize hydroxyacetaldoxime using excess hydroxylamine. They say nothing about it condensing, dimerizing, or whatever. So unless they just didn't notice or the conditions must be different, it seems that reaction doesn't occur.

Still, hydroxyacetaldehyde and derivatives look very interesting and very novel in the energetics realm from what I can tell. I found a nice looking route to it using fairly available chemicals too. Basically the idea is chlorinate vinyl acetate (pretty cheap online) in an alcohol solution with Cl2 to make chloroacetaldehyde dialkylacetal, then drip that into a NH2OH*HCl solution, basify with NaOH, extract with immiscible solvent and voila hydroxyacetaldoxime in supposedly good yields according to the patent. From there maybe react with NO2, etc and get some 2,2-dinitroethyl nitrate? That would be some crazy stuff, if it was stable.. Many other possibilities to contemplate too.

[Edited on 9-7-2010 by 497]

What he meant by that was "don't mix that material & place it within a bottle". Maintain the "Sprengle" methodology when contemplating using "Astrolite"; unless you have a container for fluids that is soft.....almost anything one can think of would have high shock impedance. The reason why he used the term "pussycats" is that the material has been so mislabeled as the "most powerful-non-nuclear explosive"....



EDIT:
I spoke with Hurst at length during the mid-1990's & he had a serious antipathy toward crap-books that maintained that Astrolite was some type of magic explosive. In fact, he believed that "dumbing down" the synthesis of explosives to a "recipe" was one of the most dangerous & ultimately stupid things anyone could do. If people did not pay their dues in reading and studying, their labs would be kitchen improvisations with commensurate consequences.
He would have had a go at our "Anders Hoveland" I'm pretty sure re: some of these threads especially the title of this one.

[Edited on 15-7-2010 by quicksilver]

Quote: Originally posted by br25

nitromethan with 80%+ H2O2 ist very powerfull and NM with TNM.Its possible to mix NM with ammonium persulfate or isopropyl nitrate?

4-nitro,5,6-triazolo-1,2,3-triazine-2,7-N-dioxide

Molecular Formula C3N7HO4

NTTO is a hypothetical target molecule which is extremely likely to be significantly more powerful than HMX, with less sensitivity. Although HMX consists of bigger molecules, NTTO is likely to have closer molecular packing because the molecule is much more polar, and because of hydrogen bonding. The aromaticity and electron-donation from the NH group to all four oxygen atoms would be expected to provide molecular stability and reduce sensitivity.

NTTO may possibly even approach the calculated power of DTTO, meaning it could exceed the power of octonitrocubane. There are structural similarities between NTTO and DTTO, and the molecular formulas, C3N7HO4 and C2N8O4 respectively, are also somewhat similar. The structure of NTTO may also be compared with LLM-116 (4-amino-3,5-dinitropyrazole), which has been calculated to be 90% as powerful as HMX, and has the formula C3N5H3O4, with two less nitrogen atoms and two more hydrogen than NTTO.

NTTO may hold promise as an excellent new high-performance energetic compound.

expected decomposition
C3N7HO4 --> (2½)CO + (½)CO2 + (½)H2O + (3½)N2

Possible Preparation
Glyoxal is condensed, under alkaline solution, with a limited quantity of nitromethane to form
O=CHCH(OH)CH2NO2.
This is then oxidized to
O=CHCH(=O)CH2NO2. A molar excess of the resulting product is then reacted with sodium hypochlorite solution to obtain
O=CHCH(=O)CH2ClNO2, with a chlorine atom added to carbon atom with the nitro group.

The O=CHCH(=O)CH2ClNO2 is reacted first with sodium azide, then with an alcoholic solution of ammonia (without water), and simultaneously cyclized in a "one-pot" reaction.
NH=CHC(NH2)=C(NO2)(N3) forms as an intermediate before transforming into 4,5-amino-6-nitro-1,2,3-triazine through a Michael-type cyclization reaction. Shevelev obtained 4-methyl,5-nitro-1,2,3-triazole in a similar reaction from the condensation of acetaldehyde with ethyl-2,2-dinitroacetate in the presence of sodium azide. (Shevelev used this as the precursor to 4,5-dinitro-1,2,3-triazole).
The one of the two vicinal amino groups of the 4,5-amino-6-nitro-1,2,3-triazine can be diazotized, with acidified sodium nitrite, and then cylized to form the adjoining triazolo ring. The 4-nitro,5,6-triazolo-1,2,3-triazine thus prepared may then be oxidized by potassium persulfate to form the final product, 4-nitro,5,6-triazolo-1,2,3-triazine-2,7-N-dioxide. This is not actually a technical name, as there is not really a "7-position" unless the compound were described as "bicyclo-hexaazo-nonane-tetraene", the N-oxide in the triazolo add-on ring not being on the nitrogen viscinal [adjacent] to the nitro group.



[Edited on 27-6-2011 by AndersHoveland]

Quote: Originally posted by AndersHoveland

NTTO is a hypothetical target molecule which is extremely likely to be significantly more powerful than HMX...

http://en.wikipedia.org/wiki/Nitroaldol_reaction

looks as though condensation of nitromethane with glyoxal results in cylization, so it may be better to start with glycolaldehyde instead, then oxidize both hydroxy groups to aldehyde after condensation. Unfortunately, this is going to mean low yields (since two hydroxy groups are being oxidized).
2-Iodoxybenzoic acid might be the ideal regent for the selective oxidation, but then one would not want to employ DMSO as the solvent as it would result in cleavage of the vicinal aldehyde.
http://onlinelibrary.wiley.com/doi/10.1002/anie.196402111/ab...

"...solution of chloronitromethane (ClCH2N02) was formed. Apparently the reactivity of chloronitromethane toward hypochlorite is not greater than nitromethane"

"Exhaustive chlorination of nitromethane under alkaline conditions yields chloropicrin (trichloronitromethane, Cl3CNO2)"

"nitromethane...Other processes for the formation of chloropicrin require an excess of sodium hypochlorite or other alkaline hypochlorite."

http://pubs.acs.org/doi/abs/10.1021/ja00522a050

http://www.springerlink.com/content/w8wt6n4063384875/

Diazotization of an amino group can allow it to link up to another amino group, in the case is vicinal amino groups, this would likely lead to cyclization to form a triazolo derivitive, unfortunately cannot find a specific reference now
Look at steps (7) and (8),
https://sites.google.com/site/energeticchemical/benzene-tria...
this forum has also discussed diazotization of 5-aminotetrazole, which leades to a --N=N--NH-- bridge.

not really related, but also found this:
http://onlinelibrary.wiley.com/doi/10.1002/qua.22517/abstrac...

As for oxidation in the final step to N-oxides, even 5-nitrotetrazole can be oxidized to the N-oxide using readily obtainable "Oxone"
http://pubs.acs.org/doi/abs/10.1021/ja106892a
The exact sites of oxidation a dependant upon the best locations for electron donation

energetic performance, comparisons with related compound
DTTO has been calculated to generate pressures of 558-567 kbar, and that is the downward revised calculation, because the previous ones were thought to be unrealistically high.
For comparison, HMX produces only 346 kbar of pressure, and octonitrocubane has been calculated at 489 kbar.
http://dodreports.com/pdf/ada513104.pdf


oxidation of amines
Also want to comment on an earlier post, reaction of secondary amines with H2O2 produces nitrones.
For example, CH3CH2CHNHCH2CH2CH3 is oxidized to
CH3CH2CH=N(-->O)CH2CH2CH3 in 89% yield.
(where the compound is an N-oxide, there are not any carbon-oxygen bonds)
http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv9...

http://www.sciencedirect.com/science/article/pii/00404039950...
http://docs.google.com/viewer?a=v&q=cache:bNaeoQOt0koJ:w...
It appears that a catalyst is required, whether tungstate, selenium dioxide, or titanium-silicate zeolite.

apparently H2O2 can be used to oxidize methylamine to
formaldoxime CH2=NOH




[Edited on 27-6-2011 by AndersHoveland]

just some ideas-
http://www.shadowrx.com/forums/showthread.php?t=1505

[Edited on 29-6-2011 by AndersHoveland]

R.A. Carboni, J.C. Kauer, J. American Chem. Society, volume 89, p2633, (1967).

Based on the above reaction which is described in literature, perhaps the reaction below would also work...




The final product would be 4-amino-pyrrolo[2,1-c]-1,2,3-triazole, which could be a useful scaffold. Presumably, it could be easily nitrated.

Although unsubstituted 1,2,3-triazole is impossible to directly nitrate, that amino group should activate the molecule to easy to nitration. 4-nitro-1,2,3-triazole, for example, is not only easily nitrated, but it is also simultaneously oxidized under the mixed-acid nitration conditions to 4,5-dinitro-1,2,3-triazole-1N-oxide.

That is to say that 4-amino-pyrrolo[2,1-c]-1,2,3-triazole would probably add three nitro groups under normal nitration conditions, without much difficulty.

The intermediate 2-[2N-connected-1,2,3-trazinyl]-acetamidinyl azide, with the structure
(H2C2N3)CH2C(=NH)N3, would doubtless reversibly cyclize into the tetrazole. The alkaline conditions both allow the cyclization, and allow it to hydrolyze back. This side equilibrium should not effect final yields. Just boil the alkaline solution until nitrogen gas ceases to be liberated.

[Edited on 1-8-2011 by AndersHoveland]

http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv4...
states that the reaction of 2-nitroaniline with hypochlorite solution produces "benzofurazan oxide" (more commonly named benzofuroxan).

Could the explosive "Fox-7" be similarly converted (by reaction with NaOCl) to 3-amino-4-nitro furoxan?
The actual chemical name for Fox-7 is 1,1-diamino-2,2-dinitroethylene.

Would further oxidation by the hypochlorite bridge the two amino groups, to yield 4,4’-Dinitro-3,3’-diazenofuroxan (DDF)?

If this route is feasible, it could potentially be a very direct and convenient way to prepare DDF, since the commercial availability of Fox-7 is increasing as a specialty research propellent. A few members in this forum have actually prepared Fox-7.

DDF molecular structure:
NO2-(C2N2O2)-N=N-(C2N2O4)-NO2,
where (C2N2O4) represents a furoxan ring.


Wikipedia describes DDF as having an extremely high detonation velocity around 10,000 m/sec, with a density of
2.02 g/cm3.

From another source (translated from russian literature):
Dinitroazofuroxan (formula C4N8O8 ) is thermally unstable, has a detonation pressure of 460kbar, and a detonation velocity of 9.7 km/sec at 1.94 g/cm3. The compound was fairly sensitive, but not extremely so.
"Dinitroazofuroxan" is just another simplified name for the 4,4’-Dinitro-3,3’-diazenofuroxan (DDF).

[Edited on 8-8-2011 by AndersHoveland]

Fox-7 can be used as a precursor for other energetic compounds.
Cannot find any references now, does anyone else have information about this?

Read that Fox-7 could be used to make dinitromethyltetrazole, although other better routes exist.

The picture below just shows what was discussed in the last two posts, the proposed oxidation of Fox-7 to DDF. Some of the members might not be able to understand the chemical naming terminology without seeing a picture.




As to the tautomerism of benzofuroxan, it is unclear whether other furoxan derivitives (such as DDF) would also show the same tautomerism,
http://www.icts.uiowa.edu/Loki/publications/browsePublicatio...

[Edited on 11-8-2011 by AndersHoveland]