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Rosco Bodine
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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 .
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Axt
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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]
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chemoleo
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-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 
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sparkgap
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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<sup>®</sup>, Plexiglas<sup>®</sup>, Lucite<sup>®</sup>, PMMA, bah, same thing....
[Edited on 7-5-2005 by sparkgap]
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Esplosivo
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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...
Theory guides, experiment decides.
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Axt
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Yah, by low MW olefins I should have added ones that actually <i>look</i> 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.
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Rosco Bodine
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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 .
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Axt
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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]
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Rosco Bodine
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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)
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J_O_H_N_Q
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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???
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12AX7
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| Quote: | Originally posted by J_O_H_N_Q
So with that in mind, what about cyclohexatriene
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...Oh, you mean benzene?
I just never heard it that way before...
Tim
[Edited on 7-8-2005 by 12AX7]
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sparkgap
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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 (~_~)
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Axt
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<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)."
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Axt
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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.
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J_O_H_N_Q
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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.
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Axt
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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.
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J_O_H_N_Q
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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.
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Axt
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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 
So yeh, It'll work.
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J_O_H_N_Q
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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.
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Axt
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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.
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J_O_H_N_Q
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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]
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Axt
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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.
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Axt
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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<sup>+</sup>(O<sup>-</sup>=N<sup>+</sup>(O<sup>-</sup>-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)
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Rosco Bodine
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practical ethylene method
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)
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Axt
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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)" <i>Chem. Rev. 2002, 102,
1019-1065</i> 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)
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