madscientist
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Reducing organic peroxides.
I have been wondering about this possibility for some time now... this idea struck me when I was trying to figure out how trioxane, (CH2O)3 (trimer of
formaldehyde) could be prepared. I was thinking that it might be that a cyclic trimeric formaldehyde peroxide is prepared, (CH2O(O))3, then is
chemically reduced to (CH2O)3. I'm not sure about how I would go about reducing an organic peroxide such as trimeric 2-peroxypropane. I know that it
is soluble in toluene. I'm thinking that it might be possible to dissolve the trimeric 2-peroxypropane in toluene, cool it, and slowly add an excess
of Na2Sx (to insure that all of the trimeric 2-peroxypropane is reduced). Of course, this would be done in an ice bath, and the temperature would be
closedly monitored. If it is possible to prepare the trimer of acetone, (CH3COCH3)3 by this method, I would be intrigued by the poI think it could be
nitrated to (CH2(NO2)COCH2(NO2))3, which I believe would be a fairly powerful energetic material. Thoughts on this, anyone? ssibility of nitrating
that compound.
I weep at the sight of flaming acetic anhydride.
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PHILOU Zrealone
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CH2=O can form various polymer as all aldehydes (cetons are not aldehydes and thus have different reactions-although there might be common response in
some reactions, most of them are different as it is the case here)!
CH2=O forms a gaseous monomer, a solid trimer (1,3,5 trioxacyclohexane or cyclotriformal (-CH2-O)3 ) and a very long polymeric chain polyformal (-
CH2-O-)n.
All solids can be found by evaporation of aqueous solutions of formaldehyde (formol):
CH2=O + H2O --> CH2(OH)2 --> (-CH2-O-)y
Aceton only exist as aceton! Evaporating aceton/water solutions gives no solid or liquid with a multimeric aceton form!
Reduction of CTAP by Na2Sx in toluen will lead to the formation of Na-S-SO-SO2-S-Na type of compounds that will release SO2 and eather result in CH2=O
gaseous monomer and (but that less possible) to the cyclotriformal!
Nitration of aceton doesn't work directly especially the 1,3 dinitration (there is more chance to get a 1,1 dinitration), oxydation is very strong too
and risks of explosions are big as it is for any 100% miscible fuel and HNO3(conc).
Typical examples are
HNO3/benzene that has the sensitivity and more power than TNB (itself over TNT).
HNO3/acetonitrile that has the power and sensitivity of NG!
HNO3/aceton will no doubt be of that kind if not more sensitive!
One of the main degradation product of aceton and HNO3 could be acetic acid, CO2, and nitromethane, dinitromethane and or trinitromethane (last two
being very dangerous) no Tetranitromethane is formed!
1,3-Dinitroaceton is a very sensitive HE, that is unstable upon storage (exorthermic polymerisation/condensations + nitro-nitrite equilibrium
degradation): explosive power between RDX and Hexanitrobenzene (8,9 - 9,8km/s)!Nitroaceton is already not very good at storage!
If ever one wants to make it he will need an alternate route instead of a direct nitration!
Once done there is big chance that making it react with H2O2/HCl would lead to extremely powerful perfect OB and also extremely sensitive peroxyde!
Peroxydation can work on two places: on the nitro group making a nitrate ester during the dynamic equilibrium shift between nitro-nitrite
rearrangement:
-CH2-NO2 <-> -CH2-O-N=O
-CH2-O-N=O + O --> -CH2-O-NO2
Then you would end up with a mix of nitro/nitrite ester/nitrate ester as hybrid or pure compounds:final product would be dihydroxyaceton dinitrate
ester:
O2N-O-CH2-CO-CH2-O-NO2 impossible to get via direct nitration (power equivalent to NG)!
Or on the C=O to make a brother of the known CDAP, CTAP and maybe CTeAP !
With nitroaceton you would get:
CDNAP, CTNAP, CTeNAP or cyclomultimers of (CH3-C(-O-)2-CH2NO2)
With 1,3 dinitroaceton you would get:
CDDNAP, CTDNAP, CTeDNAP or cyclomultimers of (O2NCH2-C(-O-)2-CH2NO2.
Of course nothing is against an hybrid of the two attacks leading on cyclo nitro, nitrite, nitrate aceton peroxydes!
Undoubtfully cyclo nitrate or dinitrate ester of hydroxy/dihydroxyacetonperoxyde would be about as strong/maybe even more as Manitol hexanitrate
ester!
CxNAP and CxDNAP could even be over the 10 km/s but very very sensitive and for sure unstable!
All those subjects have already been in my early ideas...and are on my list of things to do and to test!
PH Z
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PHILOU Zrealone
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BTW At home I have some HOCH2-CO-CH2OH;
I expect that indeed this might be a good way to go to
ON-O-CH2-CO-CH2-O-NO
O2N-CH2-CO-CH2-NO2 and O2NO-CH2-CO-CH2-ONO2
First then test those vs NG and NM and vs CTAP --> comparative datas between the 3!
Then try to peroxydise those to get nitrite /nitrate /nitro brothers of CTAP; test them vs NG/NM --> comparative datas between the 6 vs NG, NM.
Extract rules and make previsions!
Make a publication over the results!
PH Z
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madscientist
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| Quote: | -CH2-NO2 <-> -CH2-O-N=O
-CH2-O-N=O + O --> -CH2-O-NO2 |
Just how would one carry out those reactions? Simply reaction of H2O2 and -CH2-NO2 in the presence of an inorganic acid? Or something more complex? It
seems that it would be possible to convert trinitrophenol into phenol trinitrate; phenol trinitrate would be more powerful than trinitrophenol.
I have noticed that a white solid often is left behind after evaporating CH3CHO.
I weep at the sight of flaming acetic anhydride.
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madscientist
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How about reducing organic peroxides with phosphites or sulfites? If that doesn't work, is there anything that does?
I weep at the sight of flaming acetic anhydride.
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madscientist
National Hazard
Posts: 962
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Location: American Midwest
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Mood: pyrophoric
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Today I attempted to reduce liquid methyl ethyl ketone peroxide with sodium sulfite, in solution. I tried to reduce 2.9mL of liquid MEKP (density =
0.86g/cm3; details on the process I used to prepare that MEKP coming soon in the MEKP thread in Energetic Materials). This is what I did: First, I
placed 3.4g NaHSO3 in 50mL of water. I then poured in the 2.9mL of liquid MEKP. It collected in one giant blob in the beaker, and didn't seem to be
doing anything, so I began to stir vigorously. The temperature of the mixture was about 30C. I stirred vigorously for several seconds after the
mixture was simply thousands of barely-visible blobs of MEKP... at first nothing seemed to be happening. But then, suddenly, the mix became a
golden-brown color. I continued stirring, and the temperature rose to 40C (it didn't rise anymore after that).After about another minute, the mix
slowly became an aqua-blue, then a blue-green, and then took on the appearance of milk. I noticed that a small amount of an oily liquid (only visible
because of how oils shimmer on water) was on the surface; I took a tiny amount of it (collected with a stirring rod), placed it on concrete, and gave
it a solid hit with a hammer... bang! Clearly some MEKP was still present. I then did some calculations, and realized that I needed more NaHSO3 than I
had used. I decided to add a great excess: 4g. Upon addition, the mix took on a golden-brown color again. I stirred it for a few minutes, and it took
on a similar color and appearance to orange juice. After a few minutes, it returned to its previous milky appearance, with a small amount of an oily
substance floating on the surface.
My explanation: the liquid MEKP was behaving as an acid. The sodium salt of MEKP was forming, which composed the golden-brown color. Sulfurous acid
was also formed. The sulfurous acid then reduced the MEKP ion partially, transforming one of the hydroperoxide groups into a relatively non-acidic
hydroxide group - I'm hypothesizing that different variation of MEKP, in ionized form, is of a green color. Then, the other hydroperoxide group is
reduced by sulfurous acid to a hydroxide group. Sulfuric acid is formed by these reactions - end result of the reactions are sodium hydrogen sulfate,
and a variation of liquid MEKP that has two hydroxide groups instead of two hydroperoxide groups. I believe the reason for the initial milky
appearance was due to the variation of MEKP forming in the solution...
This variation of liquid MEKP should theoretically still be explosive - tests showed that it was. It seems that the peroxide chain was unaffected by
the sulfite ion / sulfurous acid.
I weep at the sight of flaming acetic anhydride.
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PHILOU Zrealone
International Hazard
Posts: 2893
Registered: 20-5-2002
Location: Brussel
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Mood: Bis-diazo-dinitro-hydroquinonic
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CH3-CH=O leaves polyacetal trimer and multimer!
Sulfites/phosphites/Fe(2+) will reduce peroxydes and Mn(2+)/ Cu(2+)....will do too!
HI will free I2!
CH2=O will certainly free HCO2H and CO2!
H2O2 will peroxydise slowly on its own without any acid help nitrite ester into nitrate!
Unfortunately:
O2N-C6H5 -/-> O2N-O-C6H5 because phenol is not an alcool but an enol
CH3-CH2OH -HNO3-> CH3-CH2-ONO2
CH3-CH=O <--> CH2=CHOH -HNO3-> CH3-CO2H
Thus even if O2N-C6H5 was peroxydised temporarly; it would rearrange and reprotonate into nitrophenol!
O2N-O-C6H5 --> HO-C6H4-NO2 (ortho or para)
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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