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Nevermore
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the cristals are very soluble in acetone, i attempted recristallization from acetone solution dumped in water, but it looks like a failure, the
solution turned white but no precipitare shown. i'll wait a few days till all the acetone evaporates to see is any will form, if not, maybe the
product was not fully nitrated
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Axt
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I think this problem also happens with MHN in acetone (ive never tried it), but will recrystalise from warm alcohol. So you could try alcohol with
nitrofructose.
Dont expect great results but, as I get the same white solution when trying to recrystalise nitrolactose from both acetone and alcohol (warm
methylated spirits). If you find the secret to recrystalising these nitrosugars be sure to post it.
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Nevermore
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by the way, is there anyone that had success in nitrating simple sugars (not poliols), as glucose, fructose, galactose and so on?
since the product i got is unsensutive to hit and burns very bad, that made me think maybe the sugar got oxidized during the nitration..
[Edited on 21/11/2003 by Nevermore]
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Axt
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Havnt tried monosaccharides, but think ive found the problem, at least for lactose (glucose-galactose).
COPAE shows nitrolactose as both octanitrate and hexanitrate, with the hexanitrate remaining in solution from recrysalisation of the octanitrate from
alcohol, though it doesnt hint as to how its extracted from the solution, perhaps evaporation, what happened after you evaporated the acetone?
Confirmed by melting the LHN in hot water (mp 70°), whereas LON's mp = 145°.
I get about 75% LHN 25% LON using KNO3 as source of nitrate. (15g lactose / 45g KNO3 / 80ml H2SO4). This could be your problem with fructose?.
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Nevermore
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that is very unlikely, i use 30ml SA 20g NH4NO3 and 6 grams fructose. I suppose some other thing was happening, did you have a test over your LHN?
hammer test, flame test?
how were the results?
[Edited on 22/11/2003 by Nevermore]
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Axt
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Deflagrates simular to nitrostarch. Seems about as hammer sensitive as PETN.
I'll get more accurate measurements when the poms piss off and the weather clears up.
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AngelEyes
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When the Poms piss off?
(we'll take the Webb-Ellis trophy with us...)
20-17: England World Champions!
The top Rugby team on the planet. 
------------------------------------------------
WTF has this got to do with this thread?? - Vulture
[Edited on 24-11-2003 by vulture]
Absolutely nothing - I just felt like shouting it from the rooftops.
Apologies if I offended...
[Edited on 26-11-2003 by AngelEyes]
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Axt
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Pommies have gone, so the sun could come back out and ....
I put nitrolactose (in matchbox) up against equal volumes of HNNM (in glass vial) and ANNM (85/15 in matchbox). Performance was pretty poor, on par
with the ANNM for damage to a 6mm Al plate and considering the non-ideal mix and low confinement of the ANNM, i'll give the Nitrolactose a VOD of
4000-4500m/s.
The movies available here - http://www.geocities.com/roguemovie3/
<img src="http://ww1.altlist.com/~52497/rogue.altlist.com/images/nitrolactose.jpg">
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Axt
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Its hard to get photos of dents, but heres the damage, nitrolactose and ANNM were about the same depth with nitrolactose a little bit wider, HNNM
results were as expected... good.
<img src="http://ww1.altlist.com/~52497/rogue.altlist.com/images/alhole.jpg">
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Smoerie
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is Nitrated Dextrose sensitive?
And how do you prefend de dehydration from your sugar when you added it???Keeping the temperature down?
Going to try it tomorrow...
greetz
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PainKilla
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Polyol Nitration experimets
I did some testing with polyols though I ahve not done all I wanted. Here is my results of malitol synth (common polyol):]
Reactants Used:
100ml (135g) H2SO4 (Rooto the gramage was off due to the H2SO4 not being anhydrous)
61g NH4NO3
38g C12-H24-O11 (Maltitol)
2000ml H2O ESU (Estimated Substance Used)
300g NaHCO3 ESU (Estimated Substance Used)
Equation:
H2SO4 + NH4NO3 --> HNO3 + NH4HSO4? (Not Sure)
C12H24O11 + 6HNO3--> C12H18N6O23 + 6H2O
62.23g (44.44ml) H2SO4 + 51g NH4NO3 --> 40g (26.00ml) HNO3 + 73.23g NH4HSO4? (I would need a bit more H2SO4 since it's not concentrated
therefore 50ml is good.)
34.4g C12-H24-O11 + 40g (26.00ml) HNO3 --> 61.4g c12-H18-N6-O23 +10.8 H2O
H2SO4 was chilled inside of a flask, in the freezer. After taking it out, the procedure followed immediately. The chilled H2SO4 was measured out to be
-8 degrees C. The flask was placed in a small-size ice bath. NH4NO3 was added in small portions, not letting the temperature jump higher than 15
degrees C. After the full addition of the NH4NO3 I pulled out thermometer and noticed white fumes, signifying that I had high % nitric, the addition
of C12-H24-O11 began. After the addition (added slowly of course) I let it nitrate for 45 minutes monitering temparature. Everything seemed normal
like any other standard nitration.
After that I did a standard filtration but I got this gum like solid that was VERY sticky. When I burned it (it wasn't dry though) it burned
slowly realsing NO2 vapor. I didn't get much product. I will be renitrating soon and doing an acetone extraction. I hope it'll work better
this time. My ETN synths go perfectly. I will buy soem more sugars next time I go to the store.
[Edited on 17-10-2004 by PainKilla]
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Rosco Bodine
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Maltitol has 9 esterfiable hydroxyls by nitration . Maltose itself has 8 hydroxyls
and forms an octanitrate ester which is possibly the most stable and useful of the
nitrosugars , having been patented by Crater , US1887290 , as a blasting cap base charge , presumably superior to
nitrolactose , US1759565 . Generally the polyol is even more stable and powerful than the parent sugar , so it would seem
that Maltitol Nonanitrate would have promise as a useful nitrated polyol . I have suggested this , but have done no experiments . The use of
ammonium nitrate with sulfuric acid has not provided
as good results in my own experiments ,
as does the use of sodium or potassium nitrate . The synthesis method which Axt reported for Erythritol Tetranitrate would probably work well for
maltitol nitration ,
if the proportions of sulfuric acid and KNO3
were multiplied by 2.25 to provide sufficient nitration mixture for the 9 hydroxyls of maltitol , ( per mole of maltitol ) 9 / 4 = 2.25 You could
compare
the mole weight of Erythritol 122.12 with
the mole weight of Maltitol 344.31 and do the math to calculate proportions which
parallel Axt's method which has proven good for ETN . It may be useful to first
dissolve the maltitol in the H2SO4 , by
portionwise additions and stirring , and then add the solid nitrate portionwise to
perform the nitration , with cooling and
stirring . Recrystallizing the product from
warm denatured alcohol or acetone or a
mixture of the two , neutralizing and then
precipitating with gradual addition of water will need to be done to obtain a stable product , hopefully in good crystalline form .
There is nothing I have found in the literature concerning Maltitol Nonanitrate .
I haven't seen it listed in any patents or
the usual comprehensive references .
Please keep us informed of what your experiments with this promising compound
reveal .
According to my math , for each 1 gram of
maltitol to be nitrated , use 3.2 grams KNO3 and 5.33 ml H2SO4 to parallel the
proportions found useful by Axt for ETN .
If the ease of nitration is similar you should get a lot of the nonanitrate as
the main product .
[Edited on 18-10-2004 by Rosco Bodine]
[Edited on 18-10-2004 by Rosco Bodine]
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Taaie-Neuskoek
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Question to Axt: What is HNNM??
I cannot find anything on google, nor on Roguesci...
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Axt
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HN = hydrogen nitrate, nitric acid. Seemed like the most logical acronym at the time, but I can now see the confusion between nitric & hydrazine
nitrate which would probably be an equally good sensitiser, if not impractical.
In that case I believe it was NM with 95% HNO3 at OB (~2:1).
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Rosco Bodine
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Axt ,
Usually NA would be the abbreviation for nitric acid , SA for sulfuric acid , PA for picric acid , ect . And generally the larger
proportion ingredient is first , although I have not always paid attention to that rule myself . So for your Sprengel explosive using nitromethane
and nitric acid , the clearest acronym would be NMNA .
When I was doing the math to determine
the molar corresponding amounts of the
nitration mixture for maltitol , based upon what was useful for erythritol as a model ,
I also reviewed the ETN thread at E&W where Axt's method and alternatives were discussed . One of the difficulties
reported was a very thick mixture , and
it is likely that difficulty will be even greater for using Axt's proportions for ETN
adapted to maltitol , so the amount of the
acid used may have to be increased a little
to facilitate a more fluid mixture which can be stirred more easily . The actual proportions which will be best for nitration of maltitol will have
to be determined from experiment , so the amounts of nitrate and acid which were
worked out mathematically should be regarded as a starting point for the minimum quantity of nitrate and acid per
gram of maltitol , not as a fixed rule .
Axt , did you ever experiment with different ratios or amounts of acid to
obtain a more fluid mixture when you were experimenting with ETN ?
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Taaie-Neuskoek
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Can't you add DCM as liquifier?
DCM is known to be nicely inert, and you don't have to wast acid for it. (in case acid is quite expensive/hard to get...)
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Axt
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| Quote: | Originally posted by Rosco Bodine
Axt , did you ever experiment with different ratios or amounts of acid to
obtain a more fluid mixture when you were experimenting with ETN ? |
Yes, that was the main factor in using that ratio, more KNO3 then that and it was too thick, and would unexpectedly solidify. Its hard to give a good
ratio for everyone, as H2SO4 is my most expensive, hard to get chem therefore the ratio I used made most use of it. Personally I rarely have probs
with 6g KNO3 to 10ml H2SO4.
Using NH4NO3 alleviated it a bit, thickens but not solid when using the same quantities (more moles), and while I cant confirm yields when I was using
AN it looked like a huge but fluffy yield. I actually got sick of filtering it and chucked a lot of it, so I cant give weights, but it definately is
worth trying if you have problems with KNO3.
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Rosco Bodine
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Methylene Chloride , DCM , (dichloromethane ) has been suggested and is a definite possibility , however it is
unknown what effect if any would it have on the nitration state achieved for the product . Since the DCM becomes a solvent carrier for the product and
also for
the nitric acid , it introduces an unknown
effect with regards to potential decomposition . Also the volatility and
toxicity of DCM is troublesome in an open
nitration reaction in a beaker so for most
people simply adjusting the mixture of
acid and nitrate is a more appealing option .
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Taaie-Neuskoek
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I my dreams I have some experience on the the synthesis of MHN,
Mannitol Hexa-Nitrate.
The problem is although, that the only proper method is AN+SA, and that I never got NA (65%) + SA to work. I nitrated mannitol in an excess NA, and
added later SA to precipitate the nitrate. I didn't get any precipitation when I added even twice the amount of SA...
Does anyone has a reasonable reason herefore? Or other idea's to try? maybe I should mix the acids and add the mannitol slowly, leaving them for
a couple of hours at -20 in the freezer. (what is suggested for SA + AN)
I'll try agian soon with a small amount agian.
The reason I ask this, is that I obtained new mannitol, and that I simply hate to purify AN from fertilliser, I never got it completely white, there
always were rests present of the Ca/Mg crap.
Nitration with 95+% NA worked nice and easy, but using that acid for this is a bit a waste...
Never argue with idiots, they drag you down their level and beat you with experience.
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PainKilla
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I didn't think maltitol had 9 things that could be nitrified or w/e. In any case, I didn't get the best prodcut but I will be dreaming the
synth on a lesser scale (no h2so4) using edited ratios (assuming 9 hydroxols are nitrable). I have a full log on ETN actaully... it will be attached.
It is actually my favorite nitrate... quite sensitive as a secondary and very pwoerful, plus the easiest nitration ever,.
Please excuse any discrepenicies though in the naming or structure or anything because I have not taken any chemistry yet , all from reading.
Structure was drawn on chemdraw freeware.
Attachment: etn.doc (34kB)
This file has been downloaded 2151 times
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Rosco Bodine
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A structural diagram for maltitol is linked below
http://apps3.fao.org/jecfa/additive_specs/docs/4/additive-06...
I have a couple of thoughts about the nitration of maltitol . It may be a more
reasonable starting ratio for KNO3 and SA to simply use the same amounts per gram of maltitol as Axt used per gram of erythritol , even though that
per gram amount would actually supply a larger excess than theory for the maltitol nitration mixture , than is the excess supplied for erythritol , in
a mole for mole comparison .
The physical considerations are more a factor because of the viscosity of the mixture . And as a general rule , the greater the number of nitro
groups to be introduced , the greater the excess of theory for the nitrating mixture must be used to assure complete nitration . It is
unknown whether that general rule applies to maltitol , but it wouldn't be any
surprise if it should prove more difficult to
accomplish the complete nitration of all 9
hydroxyls on maltitol , compared with the
relative ease of complete nitration of only 4 hydroxyls for erythritol .
IIRC the per gram of erythritol quantities for KNO3 and SA were
4 grams KNO3 and 6.7 ml SA , by Axt's method .
Since there is absolutely nothing in the literature about either the nitration or the end product , the entire matter is theoretical and experimental
, and should be done with caution , small batch sizes , being watchful of the temperature , using good stirring , followed by neutralization and
recrystallization of the product .
If I was doing this nitration I would keep the temperature of the nitration mix somewhere about 35 C as the working
temperature and about 38 C as an upper limit , unless it showed evidence of fuming and decomposition requiring a lower temperature . For time of
nitration I would
start at thirty minutes and/or or watch for the falling temperature of the mixture as an indication of the endpoint , and adjust
the time or temperature or ingredient ratios for subsequent reactions if necessary to improve yield .
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kyanite
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Maybe I'm missing something here, but I think I've read somewhere that nitric acid easily breaks down the alcohol part of sugars to form
Oxalic Acid or something...
Here we go: http://www.rhodium.ws/chemistry/formic.acid.html
Scroll down to the prep of Oxalic acid.
Maybe this has been sabotaging your yeilds all this time, also explaing the NO2 smell of TNT's experiments?
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chemoleo
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Although a valid point, I should think that the problem resides in HEATING the sample - I.e. no temperature control.
Which means the sugar is oxidised, rather than nitrated.
So if you prevent high temperatures, you won't get random oxidation to oxalic acid and others.
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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nh4clo4
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 Try nitrating antifreezes because it is a type of sugar
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PainKilla
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It is well known that ethylene glycol and propylene glycol are nitrable....
Does anyone ahve any idea why my maltitol synth does no work? I keep getting a sticky product (perhaps not fully nitrated), that does nothing. It
could also be from sulphuric destroying groups possibly but I am not certain...any input on this, I used a 100ml 94% H2SO4, 60g NH4NO3 nittration
bath. The tempearte was kept under 10C....
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