Sciencemadness Discussion Board - Pseudonitrosites

Pseudonitrosites

Axt - 5-12-2004 at 03:28

Here's a funny one. Made by the interaction of N2O3 with an unsaturated hydrocarbon. Patent US1473825 describes pseudonitrosites based on ethylene and propylene, formed by passing the gas through ether, where its mixed with N2O3 (mix of NO & NO2) which attaches forming a nitro group as well as a nitroso group which condense through a strange peroxidic bond into a dimeric structure. Both ethylene and propylene derivatives are suggested for use as base charge in detonators.

PATR 2700 gives reference to a couple more, based on butadiene and cyclohexene. It also mentions that the ethylene derivative is comparable in powder and brisance to tetryl, that aint nothing to sneeze at! Rhodium used to have the sythesis of a pseudonitrosite based on propenylbenzenes, not explosive but same procedure.

Ethylene can be made by dehydration of ethanol with sulphuric acid, CH3-CH2OH + H2SO4 → CH2=CH2 + H2SO4.H2O. N2O3 can be made by the reaction between copper (or other metal) with nitric acid, 2 Cu + 6 HNO3 → 2 Cu(NO3)2 + 3 H2O + N2O3.

Not wanting to go the EtOH/H2SO4 route (bad experiances!) I looked at MAPP gas to provide the reactive gasses. Both Propyne (CH3-C≡CH) and Propadiene (CH2=C=CH2) are likely to act on nitrogen oxides, propyne goes to dinitropropylene when reacted with NO2, but I dont know what whether NO will give it the pseudonitrosite structure as well. If propyne only has one double bond attacked its likely that propadiene will only be attacked at one bond as well, forming a different isomer then the propyne derivative of propylene pseudonitrosite. These explosives should have performance between thatof TNT and tetryl. If that made no sense, heres what I think they look like:

<center><img src="http://www.sciencemadness.org/scipics/axt/pseudonitrosites2.jpg"></center>

For the N2O3 generator, I used a glass jar containing lengths of 15mm copper pipe, through one tube in the jar was injected nitric acid, with the N2O3 coming out another tube. I fed the gasses into an upturned test tube where they mixed before bubbling out through an ether solution.

<center><img src="http://www.sciencemadness.org/scipics/axt/nitrosite.jpg"></center>

The solution turned dark green and a small precipitate of white crystals formed, no crystals formed within the testtude and a considerable amount of the MAPP gasses dissolved in the ether (it "boiled" at 22°C), therefore I dont think mixing the gasses before bubbling is necessary. The small yeiled was filtered out and dried. On ignition they turned green and burnt lazily, the yield wasnt large enough to try detonation, but at least it seemed to work.

It would be worth trying it in a more suitable vessel (measuring cylinder etc.) to get a greater yield. I tried bubbling MAPP through a concentrated nitrous acid solution (NaNO2/H2O + H2SO4), it turned dark purple but no precipitate when dunked into water. 

[Edited on 9-12-2005 by Axt]

garage chemist - 5-12-2004 at 05:29

Very interesting! Can it get even more exotic?

I wanted to say something about the preparation of N2O3 and ethylene.

The reaction of HNO3 with copper gives either NO or NO2, depending on the concentration of the HNO3. Only at narrow concentration margin, it gives N2O3.
As the HNO3 reacts, its concentration drops and the composition of the gas changes.
Your gas looks very dark red, this indicates that it consists mainly of NO2. Your acid was too concentrated!

The reaction of sodium nitrite with an acid gives pure N2O3.

2 NaNO2 + 2H+ -----> 2Na+ + 2HNO2
HNO2 decomposes:
2HNO2 ----> H2O + N2O3

Use dilute H2SO4 as the acid.
I once made N2O3 with this reaction and it was a faintly yellow gas (it became deep red on contact with air though, as the NO was oxidised to NO2 by atmospheric oxygen).

Now about Ethylene:
Sulfuric acid isn't needed, other dehydratation catalysts work, too.
Plain simple SAND is a suitable catalyst when heated strongly.
Just pass ethanol vapors (air-free!) through a strongly heated glass pipe containing some sand.
Then lead the produced gases through a condenser.
Residual Ethanol condenses, and the Ethylene can blow up a balloon for storage (if the whole apparatus is air-tight and under slight pressure).

Esplosivo - 5-12-2004 at 06:13

Quote:

The reaction of sodium nitrite with an acid gives pure N2O3.

2 NaNO2 + 2H+ -----> 2Na+ + 2HNO2
HNO2 decomposes:
2HNO2 ----> H2O + N2O3

Use dilute H2SO4 as the acid.
I once made N2O3 with this reaction and it was a faintly yellow gas (it became deep red on contact with air though, as the NO was oxidised to NO2 by atmospheric oxygen).

I don't think that that synthesis is correct. First of, N2O3 is a bluish liquid at something lower than 5 deg celcius. Secondly HNO2 IIRC does not decompose into N2O3. It decomposes into a mixture of oxides, mainly NO and NO2 (the decomposition product of HNO2 is a brown gas).

The synthesis of N2O3 is usually carried out by reacting an excess of NO(g) with oxygen or using a mixture of NO and NO2, both of which under cooling give N2O3 in the liquid state. Cooling is usually carried out in a dry ice/alcohol bath, although an ice/salt bath under -10 to -5 deg celcius should work also. (If you afford you can also use liquid nitrogen, in which case you'll obtain solid N2O3)

For the preparation of pure NO the reaction between acidified iron (II) sulfate (VI) [ferrous sulphate] with sodium nitrate (III) is usually used. Note that the method used by Axt to produce NO is also a good one. garage chemist, where are the dark red fumes in the picture? I might be going blind

but I see no such fumes. Well anyway the rxn between dilute (i.e. <50%)nitric acid with Cu fillings gives NO too - preferably excluding oxygen from the container where the rxn mixture is present.

Quote:

Now about Ethylene:
Sulfuric acid isn't needed, other dehydratation catalysts work, too.
Plain simple SAND is a suitable catalyst when heated strongly.
Just pass ethanol vapors (air-free!) through a strongly heated glass pipe containing some sand.
Then lead the produced gases through a condenser.
Residual Ethanol condenses, and the Ethylene can blow up a balloon for storage (if the whole apparatus is air-tight and under slight pressure).

Also, you're assuming that sand is completely SiO2, which it is not. This method of preparation requires high pressures and high temp IIRC, and would be rather complicated. Dehydration of the alcohol by sulfuric or phosphoric acid would be preferred. Also, correct me if I'm wrong, but SiO2 is not used in isolation as a catalyst but together with Al2O3.

[Edited on 5-12-2004 by Esplosivo]

Axt - 5-12-2004 at 06:29

Sorry that pictures confusing people! Its actually NaNO2 injected with 30% H2SO4, I tried that first. I dont think it matters that its not N2O3 as such, rather NO/NO2, as in its gasseous state its always predominatly a mixture anyway.

Yeh, so they are red fumes (not copper pipe as your seeing Esplosivo

) but its also relatively equal NO/NO2 as its formed from the nitrite!

I seemed to get a better yield using the copper/nitric method, and is less of a waste and more OTC. But I have only done it twice so how repeatable it is I dont know.

Orchards use ethylene generators to ripen fruit, wonder what catalyst they use? maybe its just sand as you mentioned Garage chemist. Its ethanol + a solid.

[Edited on 6-12-2004 by Axt]

Esplosivo - 5-12-2004 at 06:40

Well then I owe some apologies. Give the method I mentioned a try Axt. The one in which rxn of Cu with dilute HNO3 gives NO which is in turn reacted in the cold and in excess with air. Could work out better.

I have no idea what the ethylene generators use, but certain catalytic conversions do require pressure and not only heat if it were SiO2. Again I may be wrong, but it seems strange that simply boiling an alcohol with SiO2 will dehydrate it to the alkene.

Edit: Typo

[Edited on 5-12-2004 by Esplosivo]

BromicAcid - 5-12-2004 at 10:28

When I was looking for methods of making carbon tetrachloride in the chemistry abstracts, I ran across something similar to this. The reaction of tetrachloro ethylene with N2O3 or with N2O4 yields Nitro and nitroso groups added onto the bond that's broke. A small percentage of CCl4 is also formed though, hence my finding of the article.

garage chemist - 5-12-2004 at 13:24

Quote:

Again I may be wrong, but it seems strange that simply boiling an alcohol with SiO2 will dehydrate it to the alkene.

You are right, boiling ethanol with SiO2 doesn't make any reaction.
But I said that Ethanol VAPORS should be run over hot SiO2!

In the KOSMOS Chemistry set, ethylene is made via this method. I tried it and it works!
The sand needs to be very hot.
The gas generator is a long horizontal test tube, wit 10- 20 ml of ethanol (absorbed into sand) in the lower part and some dry sand in the upper part of it.
The dry sand is heated strongly and the ethanol- wet sand is heated slightly so that the ethanol vaporises and the fumes pass over the hot sand.
The gas is collected over cold water, in an inverted cylinder. Residual ethanol condenses into the water.

Try it out if you don't believe.

BromicAcid - 5-12-2004 at 13:31

The methods for producing ethylene that I've seen use a slurry of sand and H2SO4 with EtOH, I believe the sand just helps to moderate the reaction. But it may work catalytically. I don't think it would work alone though.

garage chemist - 5-12-2004 at 14:43

Sand WORKS ALONE, I will scan the synthesis from the KOSMOS manual tomorrow and post it here if you don't believe.

BromicAcid - 5-12-2004 at 14:55

I misread what you'd posted. I thought that you were speaking of a liquid/solid phase but you were talking about gaseous EtOH run over hot SiO2, yeah, that's a common type of reaction in the petroleum industry. I was too busy thinking about other methods of reaction involving the slurry of SiO2 w/ H2SO4. My mistake.

[Edited on 12/5/2004 by BromicAcid]

chemoleo - 5-12-2004 at 17:22

I just read through the patent, and it seems that the tricky bit in part is the N2O3.
Firstly it makes no mention how 'nitrogen sesquioxide' (N2O3) was produced. Secondly, and more imporantly, it states that N2O3 are used in the case of ethylene, but with other unsaturated hydrocarbons such as propylene , a mixture of N2O3 can be used together with other nitrogen oxides.
I wonder why the author came to that conclusion - and that of course immediately makes me wonder how he prepared the N2O3 in the first place - i.e. if N2O3 is a mixture of NO and NO2 at the temperatures employed (5-20 deg C), this already *constitutes* a mixture of nitrogen oxides!

Looks like it might be worth investing a bit of research in how N2O3, in the correct proportions can be made - i.e. I always had the impression that Cu, with HNO3 predominantly forms NO, where the NO2 is only formed with atmospheric oxygen.

Then - the structure of hte compound - did anyone notice, it is the peroxide circularised to the N-N (as in hydrazine), in a FOUR-membered ring?
From all I know about nitrogen, its unstable bonding to each other, coupled to a peroxide bond shouldn't really possible. Interesting also that the author proposes the structure (as shown above by Axt), but points out that it does NOT necessarily reflect the real structure.
Oh well... I have my doubts. Unless someone knows other examples where this fourmembered ring was shown to exist - will happily be educated

Then, with regard to ethylene -
I have a proper prep for it, from Gattermann. I think Mephisto uploaded it too, but it's in German. Preparation is by dehydration of ethanol with H2SO4 - will post it if interested. It's a prep designed for the organic chemist - i.e. a proper one, not some quick class room demonstration thing.
Also, I remember reading about dehydrating ethanol with heated rocksil wool - on that note, what the heck is rocksil wool? Glass wool or something?

EDIT:
I forgot, how do you know that the remaining double bond in the propene adduct (derived from the propine) does not react once again with further N2O3, to yield the fully saturated multi-nitro(so) adduct? But then, it might precipiate before it reacts.

One further thing - the author also makes no mention why N2O3 is preferred, and why not NO on its own or NO2 on its own (the latter being N2O4 at low enough temperatures). The point I am trying to make is - maybe it forms one type of adduct with NO (i.e. dinitroso ethylene), and another with NO2 (dinitroethylene adduct), while N2O3 forms the mixture (i.e. as in the structure above).

[Edited on 6-12-2004 by chemoleo]

Axt - 5-12-2004 at 18:09

The structure is also in PATR and in Rhodium. What are the alternatives? a straight dioxime peroxide (=N-O-O-N=)?

I think peroxides between two nitrogens are quite stable in contrast to C-O-O-C, check dioxime peroxides, the most simular structure I can think of, containing two carbons in a six membered ring -(C=N-O-O-N=C)-.

Another interesting find, the ether after evaporated yielded an amber coloured liquid, more dense then water and insoluble. Im assuming its the dinitro compounds.

<center><img src="http://www.sciencemadness.org/scipics/axt/dnp.jpg"></center>

EDIT: yeh, so the pic above shows that here is two products forming, theres another reference in PATR for ethylene derivative that uses N2O4 for the same product. I dont think it matters as the pseudonitrosite is the only precipitate, so easily isolated from the other products.

EDIT 2: Upload the ethylene synth!

EDIT 3: The example I found for dinitro derivative for propyne only attacked 1 = bond, thats why I think its taking on that structure. If it were to attack them both you would end up with some crazy polymer.

[Edited on 9-12-2005 by Axt]

garage chemist - 6-12-2004 at 12:45

Here's the Ethylene Synthesis from Ethanol + Sand.
It's "Versuch 438" and the apparatus picture.
Pay attention on the placement of the burner!

Sorry for the crappy picture.

Attachment: ethen001.tif (459kB)
This file has been downloaded 2058 times

Axt - 7-12-2004 at 20:00

Thanks, seems almost too easy.

Regarding the liquid product, it cannot be ignited, so I tried to make its salts to see if it was indeed the nitro's.

Some water was poured over the oily yellow liquid, then dilute NaOH was added until its sodium salt had dissolved into solution. Into this was poured solutions of lead acetate and silver nitrate. Precipitates formed immediately, black for silver and orange for lead.

The lead salt explodes very feebly, but the silver salt hold more promise, exploding with a thump, but leaving while "snowy" residue (It could be that it wasn't fully dry). The silver salt is shown below.

<center><img src="http://www.sciencemadness.org/scipics/axt/sdnp.jpg">
<a href="http://geocities.com/roguemovies7/">MOVIE</a></center>

[Edited on 9-12-2005 by Axt]

Other Pseudonitrosites!

chemoleo - 10-12-2004 at 11:42

I read something very interesting today, in Gattermann:

We all (should) know that nitromethane (alkanes) can form nitronate, i.e. it acts as a weak acid. This acidity increases with more nitro groups attached, i.e. nitroform (HC(NO2)3) has a pKa <1, which is comparable to mineral acids.

For instance, H3C-NO2, in the presence of a base, is in equilibrium with this structure H2C=N(O-)OH.
This means, the latter form (called the aci-form) can react with other electrophilic agents other than the proton, i.e. Br or nitrosyl.

HNO2 for instance reacts with nitroalkanes to form nitrolic acids, which are colourless but form deeply red salts with alkalis (which I am sure are of an energetic nature when they are lead salts).
Secondary nitroalkanes (such as 2-nitropropane) react with HNO2 to form pseudonitrosites, which are green or blue (!!) when reacting with with alkalis (this seems to be implied)

Primary nitroalkanes:

HONO + H2C=N(O-)OH (nitromethane) ---(-H2O) ----> O=N-CH2-NO2

Secondary nitroalkanes:

HONO + (CH3)2C=N(O-)OH (2-nitro propane) ---> O=N-C(CH3)2-NO2

Damn, I wish I had some nitromethane!

So, Axt, this may be something you'd want to try.

Dissolve nitromethane in NaOH (WEAK), and add KNO2 in stoichiometric amounts. Acidify with H2SO4 or something. This should liberate the HONO, which'd react with the aci-form of nitromethane, forming nitrolic acid (Which is colourless).
To this, add i.e. KHCO3, and see if the solution turns red. This should be the salt of nitrolic acid. I know nothing of its solubility however.
Lead acetate (this is likely dangerous) might be another salt to test whether you can preciptate the nitrolic acid salt.

By the looks of it, however, nitrolic acid should be fairly energetic on its own!

Re. 2-nitropropane, this should be also fairly interesting, and the colour change to green/blue should be fairly obvious.

To sum it all up: HNO2 can be used instead of NO/NO2 gas to react it straight with nitroalkanes to obtain pseudonitrosites

[Edited on 10-12-2004 by chemoleo]

Axt - 10-12-2004 at 20:53

Did you get its structure right Chemoleo! I think its an oxime, where you have a nitroso. Even still, methylnitrolic acid & its salts still possess perfect OB.

HON=CH-NO2 --> CO2 + H2O + N2

I have looked into nitrolates before, but with nitromethane, the conclusion was you can't create its sodium salt without it reacting to methazonic acid (HON=CH-CH2-NO2). Supposedly you can create it directly from HONO + NM, just havnt found the correct procedure. I have made attempts.

A vague reference is given in PATR, very unstable towards heat. Exploding below 100°C. US2401268 gives methods for everything but the nitromethane derivative. This reference would be most interesting: V. Meyer & E.J. Constan, Ann 214, 334 (1882).

Nitrosation of primary amines supposedly goes to nitrolic acids as well. I have no further info on this. Perhaps a nitrolic acid thread is in order!

The nitromethane derivative

S.C. Wack - 10-12-2004 at 22:42

from an earlier (and in English) Gattermann-Wieland. I've been meaning to scan it, it's my favorite of 36 chemistry books that I have on the shelf. But right now I'm putting Vogel's Quantitative Chemical Analysis (1989) and Qualitative Inorganic Analysis (1979) together. That'll keep me busy for awhile.

"Experiment.--Methylnitrolic acid--Nitromethane (3.2 g.) is
dissolved in 30 c.c. of ice-cold 2 N-sodium hydroxide solution and a
concentrated solution of sodium nitrite (3-5 g.) is added. Without
further cooling 4 N-sulphuric acid is run in from a dropping funnel
until the solution, which is at first deep red, has just become yellow
and does not yet turn potassium iodide-starch paper blue. The
mixture is now extracted twice with ether and the aqueous layer is
again cooled. Sulphuric acid is again dropped in until the evolution
of nitrous acid becomes distinct and the solution is then again made
so strongly alkaline with 5N-sodium hydroxide solution, that a
deep orange colour results. Once more the solution is acidified to
such an extent that nitrous acid cannot yet be detected, and is again
extracted twice with ether. The combined ether extracts are dried
for two hours over calcium chloride in a vessel kept on ice. The
ethereal solution is now transferred to a small round flask and the
solvent removed by distillation with a capillary in vacuo on the water
bath at 15°-20 °. A residue consisting of about 1 g. of well-crystal-
lised pale yellow methylnitrolic acid remains. The preparation de-
composes in the course of a few hours. Test its behaviour towards
alkalis."

It goes on to make fulminic acid and silver fulminate with HNO3 and AgNO3.

Attachment: methylnitrolic_acid.pdf (142kB)
This file has been downloaded 1805 times

Axt - 11-12-2004 at 05:03

Hmmm.

Quote from US2401267 "The foregoing reactions are usually carried out by dissolving a nitroparaffin - excepting CH3NO2 - in aqueous alkali, then adding an organic nitrite and acidifying in the cold with a mineral acid".

Interestingly this was deleted in the nearly identical patent I gave above, which is dated 1 month more recent. The pseudonitrosites are mentioned in it as well, but as the "pseudonitrole" monomer. I'll try with NaOH and see what happens, though I'm not sure if I will be able to tell the difference between methynitrolic and methazonic acid.

Couple quotes of interest:

PATR 2700 "these red salts are usually very powerful explosives".

JACS article "Sodium propylnitrolate decomposes slowly with time, as do the other alkylnitrolates"

Hopefully the heavy metal salts of methylnitrolic acid are more stable.

Axt - 12-12-2004 at 09:07

Using the method Mr Wack posted, seemed to go to plan, turning from yellow to red, then back to yellow on addition of H2SO4. Extraction with ether an evaporation in the sun resulted in decomposition and evolution of N oxides, no solid product remained.

The ether extract was mixed into a weak NaOH solution, it turned orangey red almost immediately. Straight NM/NaOH turns this colour as well on formation of methazonic acid, but it happens much slower in the concentration I used.

Lead salt was precipitated from lead acetate. On drying it wasn't energetic at all. The Pb salt precipitated from straight NM/NaOH does this as well, if its chucked onto a hotplate damp after filtration it explodes with a bang, but after dried, it looks the same, but just smoulders.

So far, the methylnitrolates look too unstable to even hold novelty value, if that is indeed what it was.

chemoleo - 12-12-2004 at 19:31

So essentially it looks like the reaction of the aci form of nitromethanol with HNO2 worked?

I.e. once you added the KNO2 to the NaOH/NM, and acidified this with H2SO4 (how strongly? did you take care of stoichiometry?), the red colour disappeared? And once you added base once again, it become red?
This would indicate the nitrolate indeed, although of course it could just indicate the plain nitronate.
Might be good to really sort out the stoichiometries.
As a control experiment, it might be best to do this with 2 nitropropanol, as this should form a green salt.

Anyway - as to the lead salt of the nitrolate - did it occur to you that you are precipitating PbSO4 as a first thing - as it is highly insoluble

? No wonder this wasn't energetic - most likely this was 90% PbSO4 and 10% Pbnitrolate.
Hmm - next time maybe acidify with HNO3, as the lead salt is soluble, while the lead nitrolate hopefully isn't. Let's hope the HNO3/NO3- doesn't somehow react with the nitrolate - I wouldn't see how, either.

As to the wrong structure you mentioned - I dont think it is, but I see why you are confused.
I.e. this is a case of tautomerism , where the HO-N=CR2 tautomerises to O=N-CHR2.
With this I can see why they called it pseudonitrosites (i.e. nitroso is N=O-C, while HON=C is oxim). I guess this tautomerism won't be possible with tertiary nitroalkanes as there isn't any hydrogen available on the neighbouring carbon... anyway...

tautomerism explains the confusion.

Oh... and nice to see that my proposed synth from above pretty much overlaps with the published one ... there is yet hope for me!

[Edited on 13-12-2004 by chemoleo]

Axt - 12-12-2004 at 22:24

Quote:

Originally posted by chemoleo
So essentially it looks like the reaction of the aci form of nitromethanol with HNO2 worked?

Yes, it seemed to, unless the extract was methazonic acid, in which case I think the same same colours would show. NM's so indecisive it annoys me greatly. Methazonic acid also readily decomposes to a red resin, so colours arnt a good indicator.

Quote:

I.e. once you added the KNO2 to the NaOH/NM, and acidified this with H2SO4 (how strongly? did you take care of stoichiometry?), the red colour disappeared? And once you added base once again, it become red?
This would indicate the nitrolate indeed, although of course it could just indicate the plain nitronate.

As far as I know the nitronate is white and methazonate red, thats why its confusing. It turns red on addition of H2SO4 (as the supposed sodium nitrolate forms), then back to yellow as it liberates the free acid. That all goes to plan.

Quote:

Anyway - as to the lead salt of the nitrolate - did it occur to you that you are precipitating PbSO4 as a first thing - as it is highly insoluble

? No wonder this wasn't energetic - most likely this was 90% PbSO4 and 10% Pbnitrolate.

I precipitated from the ether extract, which should be free of sulphate (how soluble is H2SO4 in ether?), but not free of NM/methazonic impurities, thus the indecisiveness in the product. I hate NM, really I do.

[Edited on 13-12-2004 by Axt]

Ethylene production methods

Rosco Bodine - 26-4-2005 at 22:04

Scraps of low density polyethylene , such as pieces of an empty milk jug will reportedly depolymerize to ethylene gas , if the material is slowly heated to melting and held at a temperature just above the melting point , but cooler than the point at which it forms a smoky fog above the molten material or causes darkening of the melt .

I haven't tried the depolymerization on melting of LDPE , but this would seem to be a very simple method and would utilize a material which usually is discarded as trash .

http://mattson.creighton.edu/C2H4/index.html

With regards to ethylene manufacture from ethanol and sulfuric acid , from what I have read the production of both ether and ethylene is performed in a similar way , but the temperature is kept slightly higher when ethylene is the desired product .

Ethylsulfuric acid is the intermediate in each reaction .

For an ethylsulfuric acid kept 130-140 C ,
it would seem the product which distills is a mixture of diethyl ether and ethylene ,
while if the ethylsulfuric is heated more strongly to 150 - 170 C , then the principal product is ethylene .

http://www.frogfot.com/synthesis/dietether.html

http://designer-drugs.com/pte/12.162.180.114/dcd/chemistry/e...

[Edited on 27-4-2005 by Rosco Bodine]

neutrino - 27-4-2005 at 12:54

Even a small amount of moisture will prevent polymerization in industry, so a little steam here should do the job.

A pressure cooker maybe with a little water in it ?

Rosco Bodine - 27-4-2005 at 14:52

Wow what a brainstorm , if it would work

The recyclers use superheated steam under pressure to depolymerize plastics for remanufacture .

LDPE melts at ordinary autoclave / pressure cooker temperatures I think .

I would have to double check this melting point for LDPE , unless somebody has it handy .

Update : most references I am finding give a melting point of 248 F . So far I am finding no reference to the depolymerization temperature other than it occurs below the boiling point of the melt .

Anyway , an ethylene generator for making a fair amount of ethylene

could be as simple as a pressure cooker with
some distilled water , heated to a precise
temperature and pressure , which would be regulated by the relief valve .

Presto ! A stream of ethylene and steam
being discharged . A condenser could be used to strip the moisture leaving pure ethylene gas for convenient use in synthesis .

The idea of making a stable and practical energetic material on a par with tetryl , from nothing but empty milk jugs and nitric acid and potato starch as feed materials has a certain appeal if it really is so easily done .

[Edited on 28-4-2005 by Rosco Bodine]

Axt - 29-4-2005 at 22:43

Milk jugs, starch, nitric ..... and ether

Perhaps another solvent could be used, any ideas? Though I think the pseudonitrosite procedure (if memory serves) on rhodium called for starting fluid (ether/hexane), so thats a possible source. I guess If you had ethanol/H2SO4 you could go that route but it is a lot of screwing around.

The german reference "N. J. Demjanow, Chemisches Zentralblatt, 1899 I, pg. 1064" may be interesting and provide a better more detailed procedure.

Perhaps acetylene can be substituted for ethylene, if it were to dimerise into C4H4N4O6 it would at least achieve CO balance.

Rosco Bodine - 30-4-2005 at 07:41

The reaction may occur in the gas phase
and if it does the solid product would form a condensate just the same as ammonium chloride forms a solid precipitate . On the other hand , if a solvent is required , plain alcohol is a possibility if the psedonitrosite forms preferentially instead of the nitrite ester
of the alcohol . Another possibility is the
use of a relatively inert solvent like petroleum naphtha , camp stove fuel .

And a final option certain to work , would be to start a conventional synthesis for ether
and after acummulating a needed quantity of ether in the receiver , while
delivering the distillate through an airstone or dispersion frit ,
simply raise the temperature on the distillation flask so that thereafter it is predominately ethylene which is distilling over . There is likely a specific temperature at which a
little ether will be coming over along with the ethylene to help replace any of the ether being lost to evaporation from the receiver .

Of course the receiver must be supplied simulataneouly with the delivery of the N2O3 from an adjacent airstone in the bottom of the receiver , a steady stream being supplied the entire time . The receiver should be a tall cylinder shape , with the bubblers at the bottom .

If acetone is used for the solvent , possibly a mixed product could be obtained ,
or even a possible addition compound of the two different possible nitrosites .

Axt - 6-5-2005 at 08:17

Ethylene with starch/HNO3 generation may be different, but the pseudonitrosite didn't form so readily for me, at least from MAPP gas. I mentioned in the first post that the mixing of MAPP & NOx didn't form a condensate in the test tube in which they were mixed before bubbling.

Petroleum ether is another solvent that has been used to form the pseudonitrosite of cyclohexene (<a href="http://rogue.altlist.com/banners/nitrogen_tetroxide_reactions.pdf">ref</a>

. Though for me ether is just as available (which isn't readily available either).

Cu/HNO3 has to be run hot and concentrated, getting a steady stream of NO out of it is much easier then N2O3, so starch is probably the prefered N2O3 generator (or rig an aquarium pump into a NO generator as Esplosivo mentioned, as long as the correct quantities are used).

The synthetic airstones sold for aquariums won't hold up to ether/NOx. I've taken to using a pasteur pipette stuck up the end of a PVC tube with a load of pin holes in the bubble bit.

I've been trying to think of some other compounds that may be useful, that arn't gasses! working with one gas is annoying enough but two ...

I can only think of fumaric acid, or its isomer maleic acid which may create compounds simular to <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=3590">tartaric acid dinitrate</a>. I know fumaric isn't overly soluble in water or ether (<1g/100ml). Which may be problematic. They are sold as food chems.

What other solid or liquid low MW alkenes/olefins are there?

[Edited on 6-5-2005 by Axt]

chemoleo - 6-5-2005 at 19:29

-Phorone

, mesityl oxide...
-trichloroethylene (unlikely)
-any acryl-based compound. I.e. superheating glycerol generates acrolein, H2C=CH-CHO; a gas though, which I am sure can be reduced to vinyl alcohol. same for acrylamide (solid). This might well be a good nitration target (amide bond) beyond NOx addition
-beta carotine.
-maleic acid, not just fumaric

I am sure there are more, but it's too late and I had a few, so will think about it later

sparkgap - 6-5-2005 at 21:40

Uh, chemoleo, sorry to burst your bubble, but any vinyl alcohol you might produce would spontaneously tautomerize to acetaldehyde; that is to say, vinyl alcohol effectively does not exist.

The only reason polyvinyl alcohol exists is because polyvinyl acetate can be hydrolyzed (saponified?) to it.

Yeah, phorone.

Or for that matter, any easily accessible aldol condensation product should do.

How about styrene? Can rubber be depolymerized? Plexiglas? Orlon? How about Krazy Glue? So many possibilities to speculate upon...

And chemoleo, Axt was asking for low MW olefins, so beta-carotene doesn't count. Meaning also, no fatty acids.

sparky (~_~)

P.S. Perspex®, Plexiglas®, Lucite®, PMMA, bah, same thing....

[Edited on 7-5-2005 by sparkgap]

Esplosivo - 6-5-2005 at 22:01

Plexiglass, commonly known as perspex, can easily be depolimerized by heating chips of the polymer the condensing the resulting gas of methylmethacyrlate. The methymethacrylate so formed will repolymerize due to the presence of oxygen, so make and use...

Axt - 6-5-2005 at 22:29

Yah, by low MW olefins I should have added ones that actually look explosive

, meaning have relatively good OB.

There aint many candidates, amines arnt immune from NOx, and C-CO-C compounds such as mesityl oxide, like acetone will result in <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=3033">MEDNA</a>.

Maleic goes to fumaric via N2O3, as indicated in the reference I linked to above, but its not said if nito'ey products are produced as well, or on further treatment with NOx.

Rosco Bodine - 7-5-2005 at 07:04

The patent also mentioned propylene
as useful in the same way as ethylene .

Propylene can be bought in disposable cylinders just like propane and MAPP gas .
I am pretty sure I have seen Propylene cylinders sold right alongside the better known other two , on the shelf in the propane torch supplies area of large department stores and also hardware stores . Propylene has similar high temperature output to MAPP gas , and is used for brazing and by glassworkers .
On the label it might be called " propene "
which is synonymous with propylene ,
but most definitely it is different from and more expensive , than ordinary propane .

Other solvents which could likely work in the bubble column are trichloroethylene ,
dichloromethane , and chloroform .

Ethylene still seems like the best of the
other candidate precursors for being easily made from either depolymerization of milk jug scrap , or from synthesis in a similar way as is ether made only using the higher temperature .

Axt - 3-7-2005 at 08:02

I recently tried forming an adduct with propylene oxide and NOx, 25ml propylene oxide was poured into a 100ml measuring cylinder, and NOx by way of starch/nitric acid was bubbled through it.

The PO heated up, turned yellow and turbid, and reduced to about 16ml by the end of the NOx addition. This was then evaporated of any volatiles down to 9ml.

<center><img src="http://www.sciencemadness.org/scipics/axt/propyleneoxide-no2-adduct.jpg"></center>

Presumably its mainly 1-nitroisopropyl nitrate/nitrites form first, then probably various oxidation, dimerisation, polymerisation reactions results in other products. As with the olefins a solid product is formed as well, along with a yellow tinted oil.

I havn't tried to do anything with it. Its isomer (2-nitroisopropyl nitrate) a colourless oil is listed in PATR. It possesses 75% the power (Pb block) of blasting gelatine (or 136% of TNT) and is very insensitive to impact and friction.

[Edited on 3-7-2005 by Axt]

Rosco Bodine - 3-7-2005 at 10:12

Some of these indefinite composition liquid products would possibly make nice sensitizers for ammonium nitrate .

Curiously enough , NO2 has been used for a long time as a nitration agent for
many things and NO2 is evidently what accounts for the nitrating action of nitric acid itself in nitrations where it is derived from the decomposition of the nitric acid as the nitration proceeds . Heating niter cake with additional nitrate to a high temperature can also be a source for the NO2 , as well as a way of utilizing sodium bisulfate byproduct from acid distillations .

There is also the possibility that certain catalysts may effect the course of such nitrations for the nitrosites as well as for other nitro compounds .

Attachment: GB125461 Picric Acid Manufacture.pdf (119kB)
This file has been downloaded 1270 times

J_O_H_N_Q - 7-7-2005 at 20:51

I'm assuming that the NOx substitutes onto both of the unsaturated carbons (can't think of why it wouldn't). So with that in mind, what about cyclohexatriene as a suitable reagent for pseudonitrositation?
It might give the aliphatic analogue of its aromatic cousin hexanitrobenzene?
Opinions?
Gross errors in my logic???

12AX7 - 8-7-2005 at 00:39

Quote:

Originally posted by J_O_H_N_Q
So with that in mind, what about cyclohexatriene

...Oh, you mean benzene?

I just never heard it that way before...

Tim

[Edited on 7-8-2005 by 12AX7]

sparkgap - 8-7-2005 at 05:24

Very cute, Tim.

Oh, and J_O_H_N_Q, "cyclohexatriene" is purely hypothetical. Trust me. Benzene's pi-clouds puts it up a notch over mere alkenes.

sparky (~_~)

Axt - 8-7-2005 at 16:01

<a href="http://xmovies.webtop100.net/images/nitrogen_tetroxide_reactions.pdf">The Reactions of Nitrogen Tetroxide with Organic Compounds</a> 3.09MB

"As early as 1880, Leeds (100, 101) treated benzene with nitrogen trioxide at a low temperature for several days and reported the formation of nitrobenzene, oxalic acid, and picric acid. Yields were not stated. Apparently most of the benzene as recovered unchanged."

And more regariding the alkenes/alkynes.

<a href="http://xmovies.webtop100.net/images/reactivity-of-nitrogen-dioxide.pdf">The Reactivity and Structure of Nitrogen Tetroxide</a> 5.12MB

"In solution, ethylene reacts slowly at atmospheric pressure, giving 1,2-dinitroethane and 2-nitroethyl nitrite (which in turn yields the nitrate). Propylene and the butylenes react rapidly, giving the 1 ,2-dinitro compounds and p-nitroisopropyl nitrate and nitro-tert-butyl nitrate. Addition of the first NO2 seems always to form the nitro compounds, the second NO2 may yield either nitro compound or nitrite."

"Similar behavior is shown by propylene (98); the reaction is about three times faster than with ethylene, and again follows the kinetic equation"

"At low temperatures the reaction between acetylene and dinitrogen tetroxide takes place very slowly (77)."

Axt - 16-7-2005 at 00:22

Question: How selective is the polymerisation of olefins towards catalysts. For example, how likely is the catalyst for styrene (from body filler) to act of dinitropropylene? Are there any other common catalysts to try?

Polydinitropropylene (C3H4N2O4)n by polymerising the suspected dinitropropylene (from MAPP/NO2) should be an exceptional energetic binder, possibly plasticiser.

J_O_H_N_Q - 30-8-2005 at 21:02

How about the pseudonitrosite of polybutadiene.
Should have 2 NO2 groups (maybe 1 NO2 and 1 NO) per 4 carbons.
It'll yield a nice polymeric explosive.
I'm not sure how powerful it'd be but simply by looking at it I get the feeling it'd be pretty decent. Maybe on par with TNT, by pure speculation of course.

Even better would be if one could get hold of the butadiene monomer. It should form the pseudonitrosite analogue of erythritol tetranitrate.

Axt - 3-9-2005 at 17:00

From the attachment three posts up.

"Franklin and Willtins (61) believed they obtained 1,4-dinitro-2-butene from the reaction of nitrogen tetroxide and 1 , 3-butadiene when these substances were allowed to react in various solvents or in the vapor phase."

So, CH2=CH-CH=CH2 --> O2N-CH2-CH=CH-CH2-NO2

Same goes with all other dienes it that article, they retain a double bond.

J_O_H_N_Q - 30-9-2005 at 02:05

Does anyone here have a mechanism for the formation of these pseudonitrites?
I'm thinking that the electropositive nitrogen form the NOx electrophilically adds to a terminal carbon in a double bond.
I say terminal carbon because the butadiene is said to retain a 2,3-double bond (Thank you for pointing this out AXT).
If this is so, then if we could make a solution of a reactive species of NOx, then we could bubble ethylene through it to get the ethylene derivative.
So the nitrogen species I'm suggesting is nitrosyl chloride formed in aqua regia.
The plan is that nitrosyl chloride is ONCl, not a hypochlorite. So this nitrogen is extremely electron deficient, and so should electrophilically add quite nicely, and it'll kick off a chloride, leaving an -NO group added to a terminal carbon.

What do you guys think of its potential as a nitrosating reagent?

P.S. I checked the structure wasn't something more like 'nitrogen hypochlorite' instead of nitrosyl chloride. Not sure about the reliability of the site though...
http://srdata.nist.gov/cccbdb/exp2.asp?casno=2696926
Look under "Geometric Data" almost halfway down the page.

Axt - 30-9-2005 at 02:46

I think you'll find the oxime to be the prefered tautomeric form as opposed to the nitroso group. I posted a reference to nitrosyl & nitryl chloride addition reaction with olefins in the nitrosyl perchlorate thread, also the addition of nitronium perchlorate to epoxides to form the nitrate-perchlorate diester from ethylene oxide :cool:

So yeh, It'll work.

J_O_H_N_Q - 17-10-2005 at 21:30

On the topic of ethylene generation:
Passing ethanol fumes over a catalyst of hot Al2O3 and collecting the vapors by the downward displacement of water (to dissolve any residual ethanol) works perfectly well for producing ethene.
Give it a try some time, I think you'll be happy with the results.
On the topic of suitable liquid phase to run the reaction in, what other solvents (or rather non solvents for this reaction) do you guys htink would be appropriate? Hexane perhaps? I was wondering because ethers can be a bitch to get, whereas hexane should be much easier.

Axt - 19-10-2005 at 03:32

I think its up this thread somewhere where I posted the possibility of using starting ether, try holding a can of engine starter up side down, exhausting any pressure, puncture and pour out the liquid composed of ether/hexane.

Finding pressurised propene would be the interesting one to experiment with, its mentioned in the articles that it reacts the most rapidly, where ethene reacts slower and ethyne even slower. No references to MAPP (propyne/propadiene) but I can say that it reacts slowly as well.

Propene may at least yeild a large enough quantity to determine explosive properties. Roscoe mentioned above that he may have seen it available, and internet searches list it as a fuel for brazing torches. Personally I've never seen it here.

J_O_H_N_Q - 20-10-2005 at 21:28

Maybe an Al2O3 catalyst would work for the dehydration of 1-propanol?
I can't see too many problems with using propanol instead of ethanol. Maybe a tiny bit of extra steric hindrance when the compounds coordinate to the catalyst, but not much I wouldn't imagine.

If I can organise a good test tube, I think this might be worth a try.
Any ideas on heats of reactions? I don't want some form of a runaway, although one could always just discontinue the bubbling.
Sorry if the answer's in one of those links earlier, my computer's not letting me look at them today.

[Edited on 21-10-2005 by J_O_H_N_Q]

Axt - 21-10-2005 at 04:47

I think a runaway is very unlikely, being gasses of limited solubility I dont think enough will accumulate to be a worry. I think you will get frustrated with trying to create both gasses

I used a lot to get a pitiful yield, but then ethene/propene may be different.

You could directly nitrate ethene by bubbling it through HNO3/H2SO4 to get a mixture of EGDN & nitroethylene nitrate. Which I assume can be seperated by neutralising the NEN with NaOH, decanting the solution off the EGDN then precipitating NEN with HCl.

Axt - 11-10-2006 at 15:49

Attaching article on "methylnitrosolic acid". C-nitroso compounds being rare, and the fact thats its empiric "monomer" is a monobasic acid I'm guessing it dimerises into the same structure as the pseudonitrosites. HON=CH-N+(O-

=N+(O-

-CH=NOH (thats the prefered structure given in "sidgwicks organic chem of nitrogen 3rd ed." for the pseudonitrosites).

Its also listed in PATR2700 under "nitrosomethanoxime", its potassium salt is said to explode with a loud report on heating.

I cant find a practical synthesis for formamidoxime in the literature, only one starting with HCN. Am I right in assuming one can instead condense formamide with hydroxylamine? Or perhaps a longer route starting from formaldehyde analogous to that of glyoxal + NH2OH--> diaminoglyoxime?

Attachment is old 'n german.

[Edited on 13-10-2006 by Axt]

Attachment: nitrosomethanoxime.pdf (1.4MB)
This file has been downloaded 841 times

practical ethylene method

Rosco Bodine - 2-5-2007 at 23:44

There have been some developments on the matter of
devising a simple source for ethylene , posted in another thread which is relevant to this thread .

http://www.sciencemadness.org/talk/viewthread.php?tid=7003&a...

Also , attached is the patent which was the basis of experiments described at the beginning of this thread .

Attachment: US1473825 EXPLOSIVE_FOR_USE_IN_BLASTING_CAPS.pdf (120kB)
This file has been downloaded 1125 times

Axt - 11-5-2007 at 07:54

On the structure of the "pseudonitrosites", its another one thats been restructured and renamed. As I said two posts up they have been given the structure -NO=NO-, I just downloaded an article that gives them the name "azodioxy" compounds thus in recent literature that is what you would search for. Ethylene being 1,1'-dinitro-2,2'-azodioxyethane. The articles attached.

It mentions the green colour of the C-nitroso compounds (my solution turned dark green) and the thermal decomposition of azodioxy compounds to the C-nitroso compounds. The crystals I produced turned green on ignition thus good evidence that they were the targeted compound.

EDIT: "In general, the dimers are colorless, but the monomers are blue (aliphatic) or green (aromatic)" Chem. Rev. 2002, 102, 1019-1065 Ok, mine should have been blue

oh well, maybe its more complex then blue aliphatic, green aromatic. Though oxidation of the aromatic <a href="http://www.sciencemadness.org/talk/viewthread.php?tid=5813">diaminofurazan</a> went through the green nitrosofurazan intermediate to azoxyfurazan, hmmm where did that oxygen go

[Edited on 12-5-2007 by Axt]

Attachment: Dinitroso and polynitroso compounds.pdf (506kB)
This file has been downloaded 2210 times

Rosco Bodine - 11-5-2007 at 09:33

Quote:

Originally posted by Axt
On the structure of the "pseudonitrosites", its another one thats been restructured and renamed. As I said two posts up they have been given the structure -NO=NO-, I just downloaded an article that gives them the name "azodioxy" compounds thus in recent literature that is what you would search for. Ethylene being 1,1'-dinitro-2,2'-azodioxyethane. The articles attached.

It mentions the green colour of the C-nitroso compounds (my solution turned dark green) and the thermal decomposition of azodioxy compounds to the C-nitroso compounds. The crystals I produced turned green on ignition thus good evidence that they were the targeted compound.

EDIT: "In general, the dimers are colorless, but the monomers are blue (aliphatic) or green (aromatic)" Chem. Rev. 2002, 102, 1019-1065 Ok, mine should have been blue

[Edited on 12-5-2007 by Axt]

DMSO is another possible alternative solvent for these reactions .

See US3822314 , example 16 .

This made me think of that experiment you did in the other thread also where you tried acetone peroxide
in xylene , but the xylene reacted also .

[Edited on 11-5-2007 by Rosco Bodine]

Attachment: US3822314 Preparation of Nitroximes and Nitroketones.pdf (133kB)
This file has been downloaded 1147 times

HNO3 on Acetone

franklyn - 3-2-2008 at 22:35

According to US patent 5043488 slow addition of nitric acid to acetone produces
an unknown explosive compound of undetermined structure. A sample of the novel
product was placed on a hot plate and I quote :
" When the temperature reached 40 °C, the material decomposed violently with
copious evolution of smoke and flame indicating it to be an excellent explosive. "
Ohh yeah - just the thing to replace TATB huh

Any thoughts on what this may be ? The only cited reference that is related is
Urbanski Vol I page 82 - 83

The two reagents are known incompatibles and products derived from normal
concentrations are very varied and complex, conditions of reaction affect the
processes enough to defy identification of specific pathways.

An example from this Material Safety Data Sheet warning
http://cameochemicals.noaa.gov/chemical/7198
" equal portions of acetone, nitric acid, and 75% acetic acid exploded 4 hours
after it was prepared and placed in a closed bottle."

This has a long history see the attached zip

From Hand-Book of Chemistry - 1855 page 7
Leopold Gmelin, Henry Watts

The Encyclopedia of Chemistry: Practical and Theoretical - 1862 page 31
James Curtis Booth, Campbell Morfit

This gives journal references
The Encyclopædia Britannica - 1911 page 762
Hugh Chisholm

_____________

Other references found in 1911 encyclopedia

A. Hantzsch and 0. Graul (Ber. 1898, 31, p. 2854)
described several series of salts of the nitrolic acids, with particular reference to
ethylnitrolic acid. They discriminate between the red or erythro-salts, which are
well crystallized, very explosive and unstable compounds, and which regenerate
the colourless nitrolic acid on the addition of dilute mineral acids, and the
leuco-salts, which are colourless salts obtained by warming the erythro-salts or
by exposing them to direct sunlight. These salts cannot be converted either into
the red salts or into the free acid. An intensely yellow acid salt is described, as
is also a very unstable colourless salt which could not be examined further owing
to its very labile nature. The following structural formulas are assigned to these
compounds: R CAN OH R.CCN(OK) > O R C N02K NO 2 N(:O) NO nitrolic acid;
erythro-salt; leuco-salt.

The acid salts are obtained by the addition of one molecule of alkali to two
molecules of the acid in concentrated alcoholic solution at a low temperature.
They are unstable compounds which readily split into the red salt and the free
acid on standing.

The pseudo-nitrols, RR':C(NO)(NO 2), may be obtained by the action of nitrous
acid on the secondary nitroparaffins; by the action of silver nitrite on such
bromnitroso paraffins as contain the bromine and the nitroso group united to the
same carbon atom (0. Piloty, Ber., 1902, 35, p. 3 0 93); and by the action of
nitrogen peroxide on ethereal solutions of ketoximes (R. Scholl, Ber., 1888, 21,
p. 508; G. Born, Ber. 1896, 2 9, p. 93). They exhibit an intense blue color when
in the liquid condition or dissolved in alkali and possess a very sharp smell. On
oxidation with chromic acid they yield dinitrohydrocarbons, and on reduction
with hydroxylamine (in alkaline solution) or with potassium sulphydrate give
ketoximes, RR': C: NOH (R. Scholl and K. Landsteiner, Ber., 1896, 29, p. 87).

* Note some may need to remove the .zip extension after downloading and click
to open, then select unzip program from the window menu to open. Next drag
the icon from inside the displayed folder out to the desktop and click that to
open and once again select the program from the window menu.
The contained .jpeg and .pdf should be visible then and viewable.

[Edited on 4-2-2008 by franklyn]

Attachment: pat5043488 Nitrated acetone.zip (464kB)
This file has been downloaded 1047 times

Formatik - 18-6-2010 at 19:06

The general character of the pseudonitrosites has been described by Wieland in Ann. 329, 225-268 (1903): colorless, not soluble in nearly any solvent without decomposition (except CHCl3, which solubilizes most in the cold without decomposition). When warm they are solubilized by glacial acetic acid, benzene, toluene, etc. forming nitrogen oxides, from acetic ester a small portion can crystallize unchanged. Upon storage they discolor to yellow after a short amount of time, here nitrogen oxides and HCN are released. At 30-40 C, they decompose after a few days.

-=HeX=- - 19-6-2010 at 15:49

Quick post.
This looks exciting! I may test...

Ethene... I.E. EThylene.

Use Al2O3 as catalyst. We did it in chem a while back. I will draw a pic later.

Bollocks, someone got there first.

I will have to say though, it works a charm but beware of suckback. Suckback, or delivery tube melting and overpressure = boom caused some injuries in that class. I left it with an idiot for a minute to get a gas jar when BOOM. The tube shattered in the face of the idiot. Nothing serious... Just a scare

[Edited on 19-6-2010 by -=HeX=-]

Anders Hoveland - 6-7-2010 at 15:38

http://pubs.acs.org/doi/abs/10.1021/ja00388a035
Reaction of nitrogen dioxide with alkenes and polyunsaturated fatty acids: addition and hydrogen-abstraction mechanisms.
So apparently there are two competing reactions,
2CH2CH2 + 3NO2 --> NO2CHCH2 + H2O + NO
CH2CH2 + 2NO2 --> (NO2)CH2CH2(NO2)

Is the second reaction reversible? How can I get the first to dominate?

Quote: Originally posted by chemoleo

HONO + H2C=N(O-)OH (nitromethane) ---(-H2O) ----> O=N-CH2-NO2
[Edited on 10-12-2004 by chemoleo]

What about CH3NO to make ONCH2NO ?
CH3NO can be made with NH2OH and CH2O.
"CH3NO → CH2NOH tautomerization"
pubs.acs.org/doi/abs/10.1021/jo051897r

Found some interesting alternate ways to put a nitro on an alkene, such as ethylene. Nitric oxide and "acidic Al2O3"
or use NaNO2, Ce(NH4)2(NO3)6, and glacial acetic acid.
The Nitro Group in Organic Synthesis ,By Noboru Ono
http://books.google.com/books?id=XmBZAvILOKAC&pg=PA13&am...

[Edited on 7-7-2010 by Anders Hoveland]

quicksilver - 7-7-2010 at 10:00

QUOTE:
"Found some interesting alternate ways to put a nitro on an alkene, such as ethylene. Nitric oxide and "acidic Al2O3"
or use NaNO2, Ce(NH4)2(NO3)6, and glacial acetic acid."

It's been around in various patents, etc. One of the reasons (that I could think of) it's not common is that acetic acid/ (x)NO2 is generally a more expensive route. However, if for some reason you have a healthy supply of acetic acid, you could try that with a variety of materials.
I had some acetic acid some years back & I know for a fact that it will function beyond the alkenes (nitroparaffins). Although temp control is an issue as the acid will solidify (freeze) at a rather high temp.

EDIT:
As I remember the nitration was successful.

[Edited on 7-7-2010 by quicksilver]

Anders Hoveland - 7-7-2010 at 10:31

Quote: Originally posted by quicksilver

I had some acetic acid some years back & I know for a fact that it will function beyond the alkenes (nitroparaffins).
As I remember the nitration was successful.

What exactly are you saying?
Do you mean you used glacial acetic acid to do a nitration with NO2 or KNO3 on an
alkane (ex. CH3CH3)? I would find this hard to believe.

If you mean a nitration inolving acetic acid and KNO3 on glycerine, then I would think this might be possible.

I do not think glacial acetic acid and 70% nitric acid would be compatible in a nitration procedure though.

Does anyone know exactly what "acidic alumina" means?
I found this: "There are three types of alumina that are available. The first type is acidic in character (pH 4.0)"
"Acidic Alumina
In chemistry laboratories, alumina is a medium for chromatography, available in basic (pH 9.5), acidic (pH 4.5 when in water) and neutral formulations."

[Edited on 7-7-2010 by Anders Hoveland]

quicksilver - 7-7-2010 at 13:14

I will have to post the patent (as well as notes). Rather there are a series of patents wherein materials other that the "classic mixed acids" were used to nitrate various materials. I am not saying that it would not function w/ glycerin but those that I have seen, were not.
Indeed, there is an occasionally posted nitration of phenol to dinotrophenol using sodium nitrite, sodium hydroxide, 60/25% HNO3 (& of course phenol). This indeed does produce product. It (the patent) was mistakenly reported as (application#) GB 365208 by Legard. Further investigation found this to be a typo but the synthesis DOES produce a di-nitration. UK patent application dated may 30, 1973, David Anthony Salter, Robert Simkins.

70% HNO3 has been used OFTEN with glacial acetic acid in a common RDX synthesis:

glacial acetic acid
DAPT
ammonium nitrate
acetic anhydride
-=AND=-
70% HNO3
[William J. Sukasavage, Las Vegas NV Aug 28, 1992 application] Patent owned by US Army

EDIT

QUOTE:
"Does anyone know exactly what "acidic alumina" means?"

In what context was this used? It sounds like 19th century reference.

[Edited on 7-7-2010 by quicksilver]

Anders Hoveland - 7-7-2010 at 16:02

http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv2...

Methyl-Ethyl ketone MEK is readily available as a paint thinner. CH3CH2C(=O)CH3
Add NH2OH which will condense with the product in the picture to form the double oxime. CH3C(=NOH)C(=NOH)CH3
This should react with NO2 gas, and then be oxidized to
2,2,3,3-tetranitro butane
This would be powerful, but might be moderately sensitive.

dioxime.bmp - 155kB

497 - 7-7-2010 at 21:26

Yes this reaction is known. Sadly the yields from the oxidation step seem to be low in literature.

I was going to say it would be interesting to try with phloroglucinol trioxime to make 1,1,3,3,5,5-hexanitrocyclohexane but I found literature saying it instead forms hexanitrobenzene.. Maybe this is a useful synthesis of tetranitrobenzene? The yields would probably be bad though.

You might be able to nitrosate cyclohexane-1,4-dione and react with hydroxylamine to get 1,2,4,5-cyclohexanetetroxime. Then to 1,1,2,2,4,4,5,5-octanitrocyclohexane? Too unstable I suppose.

[Edited on 8-7-2010 by 497]

Anders Hoveland - 8-7-2010 at 12:57

Quote: Originally posted by quicksilver

there is an occasionally posted nitration of phenol to dinotrophenol using sodium nitrite, sodium hydroxide, 60/25% HNO3 (& of course phenol).

70% HNO3 has been used OFTEN with glacial acetic acid in a common RDX synthesis: glacial acetic acid, ammonium nitrate,
acetic anhydride, 70% HNO3

Did you mean that sodium nitrite and anhydrous dry NaOH alone is capabable of nitrating phenol? If this is the case, I have seen amine groups being added to trinitro benzene by NH2OH and fused KOH used to dehydrate/ make the amine condense on (forming trinitro, triamino benzene) in moderate yield. Or did you mean that both nitric acid and NaOH were used in the nitration? Why use the NaOH?

70% HNO3 is used in the RDX with acetic acid, but the nitric acid is slowly added, and it immediately dilutes itself in the acetic acid or reacts to form the nitramine before the concentration gets high enough to start oxidizing the acetic acid. I know from experience that 5% HNO3 solution is incapable of dissolving copper foil after 2 days, but I suspect that the copper would eventually dissolve if given enough time. The more HNO3 is diluted, the less the equilibrium favors the oxidizing nitronium ions.

Quote: Originally posted by 497

it would be interesting to try with phloroglucinol trioxime to make 1,1,3,3,5,5-hexanitrocyclohexane, but it instead forms hexanitrobenzene.. Maybe this is a useful synthesis of tetranitrobenzene? The yields would probably be bad though.

I do not think there is any particular reason why the yields would not be very high, whatever byproducts would form would probably be stuff like 1,1,3,3,5,6-hexanitro cyclohexene, the molecule containing only one double bond between two carbon atoms. The mix of products need not necessarily be separated from eachother to be useful. The 1,4-oxime of quinone could likely react with NO2 to make 1,4,-dinitro, 2,5-dinitroso benzene, which when oxidized would afford the tetranitro. Or instead, be reduced with bisulfite to 1,4-dintro, 2,5-hydroxylamino benzene that could be used for energetic salts. Or tetranitro benzene heated with NaN3 would make the 1,2,4,5-di furoxan of benzene
(NaN3 used in 'Megalomania's synthesis of 'Cl-22'), which could then have another nitro group easily added. All these routes are probably obvious to most readers.

Quote: Originally posted by 497

You might be able to nitrosate cyclohexane-1,4-dione and react with hydroxylamine to get 1,2,4,5-cyclohexanetetroxime. Then to 1,1,2,2,4,4,5,5-octanitrocyclohexane? Too unstable I suppose.

Was a typo mistake was made? If you nitrosated cyclohexane-1,4-oxime (with NO+ cations) you would likely get 1,2,4,5-tetra nitroso benzene. If you reacted cyclohexane-1,4-dione with NO and NO2, then up to two NO or NO2 groups would likely be added to positions
#2,3,5,and 6. This would be random. Condensing this with NH2OH, and then using NO2 on the resulting oxime, and finally oxidizing any nitroso groups to nitro, would presumably give a final product of poly-nitro hexane. I am fairly certain that anything pass 6 nitro groups would be highly unstable. What do you mean "nitrosate cyclohexane-1,4-dione and react with hydroxylamine"? I do not understand.

1,1,2,2,4,4,5,5-octanitrocyclohexane would probably be just a little more stable than nitroglycerine, and more powerful than HMX.

[Edited on 8-7-2010 by Anders Hoveland]

quicksilver - 8-7-2010 at 14:31

A long time back; certainly 4 years ago, there was a long thread that detailed all the things one could do with 70% HNO3; all the nitration, the labs (fulminate), etc, etc.....When you first started writing about 70% acid I looked for that but couldn't find it. Additionally I don't know if deletions take place to maintain a certain data-size footprint on the forum, but I do remember the thread.

497 - 9-7-2010 at 07:17

Quote:

What do you mean "nitrosate cyclohexane-1,4-dione and react with hydroxylamine"? I do not understand.

Sorry, I didn't explain very well there. I meant do the style of nitrosation that adds an oxime adjacent to a ketone, as mentioned earlier in the thread. I know that doing that on cyclohexanone will yield 2-oximinocyclohexanone, and I am assuming the it would also occur on both sides of cyclohexane-1,4-dione to yield 2,5-dioximinocyclohexane-1,4-dione.. maybe also the 2,3-dioximinocyclohexane-1,4-dione but I'm guessing that is less likely. The treating the remaining ketone with NH2OH to yield the 1,2,4,5-tetraoxime... from there treat with NO2 then H2O2 as usual to hopefully end up with the octanitro product. My logic is, if it works for dimethylglyoxime, it should work here.. Also, I know 1,1,4,4-tetranitrocyclohexane exists..

Anders Hoveland - 9-7-2010 at 08:53

It all seems like it might work, but the big disadvantage is: how would you make the
dioximinocyclohexane-1,4-dione? This does not seem to be within the capabilities of even the most enthusiastic of basement experimenters.

-=HeX=- - 9-7-2010 at 09:10

Anders: I know a few companies that will custom - synth chemicals for you, as long as the chemical is not illegal. No questions asked at all. They deliver to home and all

Sadly, it seems to be Europe only

That puts it in reach... Though perhaps not of my budget. Just wait till I get *that* job

As for the OT hexanitrobenzene--->tetranitrobenzene, how do we strip off the Nitro groups and put Hydrogen on? I know a reduction (partial) would only cause it to be, at closest, Tetranitro-diaminobenzene

497 - 9-7-2010 at 12:33

Quote:

It all seems like it might work, but the big disadvantage is: how would you make the dioximinocyclohexane-1,4-dione?

I'm a little confused as to what you mean.. The dioximinocyclohexane-1,4-dione would be produced by treating cyclohexane-1,4-dione with a mixture of isopropyl nitrite, HCl and DMSO for example, although there are other reagents that could be used.

If you meant, where would the cyclohexane-1,4-dione precourser come from, well that is a bigger problem. It might be easiest to go hydroquinone -> p-benzoquinone -> p-benzoquinone diketal, then hydrogenate that to cyclohexanedione diketal, which could be directly nitrosated since the ketals would hydrolyze in situ. There are references for basically all the steps, and yields should be good in all steps except the final oxidation steps. The hydrogenation would be the only problematic step since it would require a catalyst and probably pressurized hydrogen.. But home made Urushibara nickel catalysts are really easy. Add in a little hydrogen from a home made electrolysis cell and it could be done. No exotic reagents required.

Man if it was stable enough I bet the octanitrocyclohexane would be a really kick ass explosive. Near perfect OB. And of course there are always possibilities for adding even more power/stability by substituting the two unsubstituted carbons with something.

Anders Hoveland - 10-7-2010 at 15:06

I do not think it would be an ideal explosive. The chemist would have little control over exactly where the nitro groups would be added to the molecule, so some of the molecules might have all the nitro's clustered toward one end, some molecules might have only one or two nitro groups, and others might have way too many. This would give the mixture unnecessary instability and extreme sensitivity if it was be nitrated enough to be significantly powerful. I think it is probably too complex to be very useful. Consider instead other stuff like trinitro ethane.
If you have access to CH3CH2CH=O then you could condense it with NH2OH, then bubble in NO2, then possibly oxidize with H2O2 (if that would work) and get 1,1,1-trinitro propane.

Boffis - 28-2-2018 at 09:55

Quote: Originally posted by Axt

From the attachment three posts up.

"Franklin and Willtins (61) believed they obtained 1,4-dinitro-2-butene from the reaction of nitrogen tetroxide and 1 , 3-butadiene when these substances were allowed to react in various solvents or in the vapor phase."

So, CH2=CH-CH=CH2 --> O2N-CH2-CH=CH-CH2-NO2

Same goes with all other dienes it that article, they retain a double bond.

Does anyone alive today have a copy of or know the reference for "the attachment three post above" as I am trying to find the Franklin and Willtins reference here but I can't find any Willtins in the author citation and wondered if it is a spelling mistake