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DennyDevHE77
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Transesterification and purification of ETN from mixed sulfoesters
Hello everyone, I'm new to the forum, so if I'm asking stupid questions, then tell me, I'll fix it)
To begin with, let me explain what caused this question, you see, I have been doing PETN for quite some time. As you know, one of the methods for its
production is nitration with sulfur-nitrogen nitro mixtures in one stage. But at the same time, along with PETN, various mixed sulfoethers are
obtained. But they can be removed. To begin with, after adding all the pentaerythritol to the reaction mass, PETN is heated to ~50°C
(transesterification reaction), for 20 minutes, thus part of the sulfoesters are converted to PETN, increasing the yield. The other sulfoester
(dinitrate disulfate) is removed by boiling the PETN in a Sodium bicarbonate /MgO solution until the foam disappears. Of course, then
recrystallization is carried out from acetone with the addition of carbonates to remove the acid inside the crystals.
It should be noted that the transesterification procedure is also carried out for other nitroesters, for example, mannitol is also heated to 50°C
for an hour.
And so, I got erythritol. Deciding to first study the practice of its production here, I discovered two things:
1) No one for some reason carries out the transesterification reaction. Hence the low yield of the majority (30-50%) instead of the prescribed
~90%, at least it seems to me  In fairness, I found one study where it was heated
up to 35°C, but at 35°C interesterification is just beginning, but it goes quite quickly only at 50-60°C. So it's weird...
2) Nobody cleans it from sulfoesters? Why? After all, they affect power, chemical stability.
For me, the question is so acute, because once, due to a highly diluted acid, I received a mixture of PETN: sulfates (50:50). The explosion was weak,
the syringe that cut down the tree earlier only tore off the bark (albeit deeply). I'm afraid of getting ETN contaminated with sulfates.
I did not find answers to these questions either on the forum or in research (on the other hand, they were more devoted to mixtures, explosive
properties and not synthesis). If this has been discussed somewhere, send me a link, and I will delete this topic so as not to clog the wall
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underground
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Can you give more details of your synthesis?
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DennyDevHE77
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About the synthesis of PETN? Well, I usually get it with a mixture of nitric acid 70% and 94% sulfuric acid (33 ml and 19 ml). or (35 ml and 37 ml if
nitric acid 58%) per 10 g of pentaerythritol. These ratios are taken from Urbansky, and are "ideal". That is, any change in these ratios will lead to
either a drop in yield, or oxidation, or unnecessary waste of pentaerythritol.
By the way, I did not find similar ratios for ETN. Like the regions of the formation of ETN by nitration mixture  Generally speaking, I haven't had any significant problems with PETN. Now I am collecting information about ETN,
before its manufacture.
[Edited on 14-7-2023 by DennyDevHE77]
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underground
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Pentaerythrilol has a molar mass of 136,15 g/mol
Erythrilol has a molar mass of 122,12 g/mol
10g of Pentaerythritol are 0,073448 moles
0,073448 moles of Erythritol are 8,97g
So you use the same procedure but instead of 10g of Pentaerythritol you use 8,97g of Erythritol
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DennyDevHE77
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Um, I don't quite understand what you're saying? Thank you of course. But I just wanted to know why ETN is not transesterified at elevated
temperatures and how it is desulphated.
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OneEyedPyro
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Perhaps I'm not sure what you're asking here but contaminants likely to be in crude ETN including lower nitrates are water soluble while the
tetranitrate is insoluble. Impurities are easily removed via the dissolve and crash type recrystallization.
Simply dissolve ETN into a solvent like methanol, ethanol, acetone etc that's heated to 50C. Then slowly pour it into water containing a bit of sodium
bicarbonate under strong stirring, repeat the process once more with distilled water and you've got essentially 100% pure ETN.
Heating toward the end of nitration is a bad idea since ETN is not particularly chemically stable, you could VERY easily have a nitration and
dehydration related thermal runaway at those temps and will yield less even if it doesn't runaway.
Start at 0C with strong continuous stirring and let it come up to no more than about 20C and hold it there through the majority of the nitration . How
long to nitrate is debated but 3 hours seems to be fine.
[Edited on 14-7-2023 by OneEyedPyro]
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Hey Buddy
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To be clear, it's unclear what you're communicating in the post. Whether you want to report to us about the method you're describing, or checking to
see if other people use this method you use? Most people I'm familiar with use a variation of a nitrate salt/H2SO4 procedure for nitrate esters.
That's the standard for high production. Even companies like ATK have experimented with that route. As far as I know, ATK isn't heating the reaction
mixture in nitrate salt productions of PETN, TEGDN/DGTN, TMETN,NG or BTTN. For PETN, they get w/ 8NH4NO3/H2SO4 a 62% yield. The reaction time is 2
Hours at ambient temp.
I make some nitrate esters sometimes, if there is a method to increase yield and stability, I would like to read about it. You can just write a
summary about it for us to read about.
I don't use any heating at all on nitrate esters until recrys. Just for a margin of safety for unaware future readers, because "heat" and "ETN" in the
same posts makes me nervous for the unaware:
ETN is very different from PETN, its mechanical sensitivities are a little higher and on exposure to heat, it has primary explosive character. The
thermal characteristics set ETN apart from PETN. The other aspect that sets ETN apart is its melt phase at low temp. @65 C ETN melts and its
mechanical impact sensitivity increases approximately 15x while in fluid phase and then returns to normal mechanical sensitivity after complete
resolidification. I also believe ETNs thermal response sensitivity is also increased during melt phase. For me personally, this is not a small
character difference, it puts ETN in it's own class, straddling primary secondary explosive.
Most of the work on ETN is short, and sparse.
I will post some papers that I think are useful for people really trying to get a better understanding of ETN. As well as the original Du Pont patent
and the ATK publication on their nitrate ester via nitrate salt tests. These publications contain 99% of referenced literature that anyone uses to
prepare ETN. The papers will give you a thorough understanding of how people commonly prepare ETN. You can check some of it out and see how it differs
from your methods and then tell us what may or may not improve yield and why. I have never heard of sulfoesters and have only ever glanced at
transesterification... You will have to convince me that an alternate procedure is better though, because I'm satisfied with simple ETN that has long
shelf life.
Attachment: ETN EXPLOSIVE PROPS MATYAS.pdf (558kB)
This file has been downloaded 285 times
Attachment: ETN Performance Properties MANNER.pdf (645kB)
This file has been downloaded 202 times
Attachment: ETN MELT CAST SENSITIVITY CHAVEZ.pdf (295kB)
This file has been downloaded 168 times
Attachment: ETN_du-pont.pdf (177kB)
This file has been downloaded 171 times
Attachment: ATK_Prep_Nitrate_esters_Polyols_STRAESSLER.pdf (780kB)
This file has been downloaded 198 times
Attachment: ETN_AN_sensitization_KUNZEL.pdf (213kB)
This file has been downloaded 187 times
Attachment: ETN Frag velocities.pdf (841kB)
This file has been downloaded 385 times
Attachment: ETN_Thermal_Decomp_OXLEY.pdf (988kB)
This file has been downloaded 366 times
Attachment: etn eutetics oxley.pdf (4.4MB)
This file has been downloaded 331 times
[Edited on 15-7-2023 by Hey Buddy]
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DennyDevHE77
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I am very sorry that my post came out incomprehensible. Perhaps I should have phrased it differently.
Let me explain again, using the example of my long work with PETH, I decided that work with other nitroesters (nitromannite, nitroglycerin, ETH)
should be similar. That is, the processes of nitration, purification processes, recrystallization, etc. should be similar. That's why I told at the
beginning of my post about my work with PETN. I mean, I kind of wanted to say, "Hey guys, I haven't worked with ETH yet, but I've worked with PETH and
it's like this, will ETH be the same?"
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OneEyedPyro
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Quote: Originally posted by DennyDevHE77  | I am very sorry that my post came out incomprehensible. Perhaps I should have phrased it differently.
Let me explain again, using the example of my long work with PETH, I decided that work with other nitroesters (nitromannite, nitroglycerin, ETH)
should be similar. That is, the processes of nitration, purification processes, recrystallization, etc. should be similar. That's why I told at the
beginning of my post about my work with PETN. I mean, I kind of wanted to say, "Hey guys, I haven't worked with ETH yet, but I've worked with PETH and
it's like this, will ETH be the same?" |
The manufacture of ETN is similar to PETN, the purification procedures are also similar.
ETN is not as physically or chemically stable as PETN and you cannot treat them interchangeably in synthesis or handling.
Refer to the post I left above earlier. If that doesn't answer your question, I'm not sure what will.
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DennyDevHE77
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Hey Buddy, thanks for all the links, I'll study them, I think I won't have any questions later. You also say you haven't heard of sulfoesters. I can
talk about them using the example of PETN. Well, obviously like nitroesters formed by nitric acid, sulfoesters are formed by sulfuric acid. for
example, earlier PETN was obtained by a two-stage method, first it was dissolved in sulfuric acid (pentaerythritol sulfate was obtained), or rather,
pentaerythritol disulfate, trisulfate, tetrasulfate were obtained. That is why they are called "mixed". Then they are nitrated with fuming nitric acid
at 55-60°C. With a one-stage method on a sulfur-nitrogen nitro mixture, these sulfates are also formed, but in a smaller amount.
However, during transesterification, pentaerythritol dinitrate disulfate is obtained, even at 55-60°C it does not completely turn into PETN, and
prolonged boiling in a 1% solution of sodium bicarbonate is required (boiled in autoclaves in industry), or magnesium oxide, or heating to 90°C with
calcined soda. Boil until the foam disappears. This is followed by recrystallization from acetone. If you immediately try to recrystallize PETH in
acetone, this will not remove all pentaerythritol dinitrate disulfate, which will affect the power and stability of the final product. Therefore, it
is desirable to heat PETN, this allows you to increase the yield to 92%.
Mannitol sulfates are also formed when it is nitrated, and it is also heated to 50°C for greater yield and stability. But you can not boil it, when
boiled with water, it quickly denitrates. And in any case, mannitol hexanitrate is very unstable. Stabilizers (centralites) are added to it, and
anyway, as far as I know, acidity rises after six months or a year.
And even when glycerol is nitrated with a sulfuric acid mixture, mononitromonosulfates, dinitromonosulfates and mononitrodisulfate are formed. But
they are easily destroyed by hot water. That is, it is enough to mix nitroglycerin with a hot double volume of 2% sodium bicarbonate solution, blow
the emulsion for 3-5 minutes with compressed air, and get a pure product.
In general, knowing all this, I decided to find out on this forum on cleaning ETH, citing as an example my experience with other nitrates, especially
with PETH. To tell me how much the synthesis of ETH coincides with the synthesis of the same PETN. I thought that ETH, like PETN, needs to be heated
to 50-60°C, and I wondered why no one on the forum did this to bring the output to 92%. But apparently I was mistaken, and it is impossible to adjust
the specific methods for obtaining one substance to another, even similar.
[Edited on 15-7-2023 by DennyDevHE77]
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DennyDevHE77
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| Quote: Originally posted by OneEyedPyro | | Quote: Originally posted by DennyDevHE77 | I am very sorry that my post came out incomprehensible. Perhaps I should have phrased it differently.
Let me explain again, using the example of my long work with PETH, I decided that work with other nitroesters (nitromannite, nitroglycerin, ETH)
should be similar. That is, the processes of nitration, purification processes, recrystallization, etc. should be similar. That's why I told at the
beginning of my post about my work with PETN. I mean, I kind of wanted to say, "Hey guys, I haven't worked with ETH yet, but I've worked with PETH and
it's like this, will ETH be the same?" |
The manufacture of ETN is similar to PETN, the purification procedures are also similar.
ETN is not as physically or chemically stable as PETN and you cannot treat them interchangeably in synthesis or handling.
Refer to the post I left above earlier. If that doesn't answer your question, I'm not sure what will. |
I already looked at your post. Unfortunately you were right
In general, I will have to be content with an output of 50-60%. Not very profitable, with a common ratio of 200 g of NH4NO3, 300 ml of sulfuric acid,
and 60 g of erythritol. I should get less than 100 g of ETH. After all, the same PETN with 300 ml of sulfuric acid comes out > 300 grams
But the PETN cannot be melted
Although I may be able to raise the yield with acetic anhydride.
For example, dissolve it in 70% nitric acid and warm it. So that it hydrolyzes, and I get a solution of nitric acid in glacial acetic acid with acetic
anhydride ...
[Edited on 15-7-2023 by DennyDevHE77]
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Etanol
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This is very very dangerous in the case of ETN!
How did you determine the presence of sulfates?
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littlesky
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Interesting ideas.
In fact, the ester exchange method is very good for synthesizing ETN. This was mentioned in a Chinese literature. They dissolved Erythrose in
concentrated sulfuric acid to obtain a pale yellow liquid (possibly the Organosulfate of Erythrose), and then added fuming nitric acid (or a mixture
of industrial nitric acid (65-68%)/concentrated sulfuric acid) to this liquid to obtain a high yield (about 87%). A fairly pure product is obtained by
removing acid from acetone and sodium carbonate solutions. I have been using this method to synthesize etn since.
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DennyDevHE77
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At that time, instead of 58% nitric acid, they sent me only 42%. Without knowing this, I prepared a mixture of 140 ml of nitric acid and 148 ml of
sulfuric acid (94%), for 40 g of pentaerythritol. The process of preparing PETN was no different from normal, 58% nitric acid, the mixture also
thickened, just warmed up, in general, it looked like the most typical nitration. At that time, I did not heat PETN for sulfate transesterification.
Yield then was 82g, I almost didn't lose PETN at the stages of fltration, recrystallization, etc. I think I lost 1-2g at these stages.
Then there was a very weak explosion. Who just tore the bark off the tree. (before that, a PETN made at 95% WFNA cut down the same tree)
Wishing to understand this, I looked into the specialized literature. There it was indicated how PETN is cleaned in industry, in particular, about its
boiling in weakly alkaline solutions.
Then I had 70g of PETN left, I made two liters of 1% sodium bicarbonate solution and began to heat PETN in it, when the solution boiled, a huge amount
of foam floated to the surface. After an hour and a half of boiling and regular stirring, the foam was gone, I filtered out PETN, and it turned out
that 42g of it remained.
What else could it be but sulfates that were destroyed during the boiling process? PETN can be contaminated, in addition to them, by under-nitrated
molecules, BUT, mono- and di-nitrates are soluble in water, trinitrate (PETRIN) is generally liquid. So besides sulfates, there could hardly be
anything. A little later, I suggested that perhaps PETN was simply hydrolyzed during boiling. But then taking 100 g of purified PETN obtained at WFNA,
and boiling them for an hour and a half in 2.5 liters of 1% soda solution, I filtered out 98 g of PETN. And maybe I lost them on the filter.
Since then, I always heat PETN to 50-55°C, then boil it in a sodium bicarbonate solution, and finally boil it in acetone under reflux (100g PETN in
340 ml acetone with the addition of 4g baking soda), boil until the PETN solution in acetone is turns dark yellow. As I understand it, boiling in
acetone also removes sulfo-ethers, but only in small quantities, so boiling in a few liters of ordinary water is indispensable.
Usually my yield is 86g with 40g pentaerythritol. With 58%, 65%, 70% nitric acid. The main thing is to add the correct amount of sulfuric acid.
[Edited on 16-7-2023 by DennyDevHE77]
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DennyDevHE77
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| Quote: Originally posted by littlesky | Interesting ideas.
In fact, the ester exchange method is very good for synthesizing ETN. This was mentioned in a Chinese literature. They dissolved Erythrose in
concentrated sulfuric acid to obtain a pale yellow liquid (possibly the Organosulfate of Erythrose), and then added fuming nitric acid (or a mixture
of industrial nitric acid (65-68%)/concentrated sulfuric acid) to this liquid to obtain a high yield (about 87%). A fairly pure product is obtained by
removing acid from acetone and sodium carbonate solutions. I have been using this method to synthesize etn since. |
Please tell me your method. I tried to implement the same method just last night. I took 10g of erythritol, and added them to 50g (27g) of sulfuric
acid (at room temperature), after 15 minutes, when the erythritol was almost completely dissolved, I poured this solution into 75 ml of 70% nitric
acid (extra pure for analysis) with the addition of 30 ml of conc. sulfuric acid. Quite quickly, a white powder began to form inside the reaction
mass. I began to heat the mixture in a water bath, at about 55°C the powder dissolved, it seemed as if ETH had decomposed, although some kind of
"oil" was visible floating in the reaction mass. I sat down for 15 minutes of heating at 50-52°C, I poured the nitro mixture into 700 ml of ice
water. A fine white precipitate fell out, but in a very small amount. 700 ml of water is only slightly cloudy.
Perhaps I warmed too little, only 15 minutes, instead of 30-45 minutes. Or I used insufficiently strong nitric acid.
[Edited on 16-7-2023 by DennyDevHE77]
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OneEyedPyro
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| Quote: Originally posted by DennyDevHE77 |
Please tell me your method. I tried to implement the same method just last night. I took 10g of erythritol, and added them to 50g (27g) of sulfuric
acid (at room temperature), after 15 minutes, when the erythritol was almost completely dissolved, I poured this solution into 75 ml of 70% nitric
acid (extra pure for analysis) with the addition of 30 ml of conc. sulfuric acid. Quite quickly, a white powder began to form inside the reaction
mass. I began to heat the mixture in a water bath, at about 55°C the powder dissolved, it seemed as if ETH had decomposed, although some kind of
"oil" was visible floating in the reaction mass. I sat down for 15 minutes of heating at 50-52°C, I poured the nitro mixture into 700 ml of ice
water. A fine white precipitate fell out, but in a very small amount. 700 ml of water is only slightly cloudy.
Perhaps I warmed too little, only 15 minutes, instead of 30-45 minutes. Or I used insufficiently strong nitric acid.
[Edited on 16-7-2023 by DennyDevHE77] |
I don't believe erythritol can survive in concentrated sulfuric acid at room temperature without simply being dehydrated nor do I believe ETN can
survive in a nitration mixture at 50C. Like I've been saying, erythritol and ETN are not very strong molecules. It seems you assume this reaction can
be treated like that of TNT or picric acid, it cannot.
Heating the nitration mixture to 50C is fruitless as you've found out, it is also dangerous.
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Tsjerk
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| Quote: Originally posted by DennyDevHE77 |
What else could it be but sulfates that were destroyed during the boiling process? PETN can be contaminated, in addition to them, by under-nitrated
molecules, BUT, mono- and di-nitrates are soluble in water, trinitrate (PETRIN) is generally liquid
[Edited on 16-7-2023 by DennyDevHE77] |
Do you mean to say there can't be under nitrated PE in your PETN because you crashed the PETN in water? I think they are just not that soluble, so
they crash out together with the PETN and afterwards when you boil in such a large volume of water they do dissolve. No need for sulfate ester
hypothesis, just some not fully nitrated PE.
Did you do any cleanup besides crashing the nitration mixture in water or do you just assume that the initial crude product had to be pure and when it
wasn't it had to be sulfates?
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Etanol
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| Quote: Originally posted by DennyDevHE77 |
Please tell me your method. I tried to implement the same method just last night. I took 10g of erythritol, and added them to 50g (27g) of sulfuric
acid (at room temperature), after 15 minutes, when the erythritol was almost completely dissolved, I poured this solution into 75 ml of 70% nitric
acid (extra pure for analysis) with the addition of 30 ml of conc. sulfuric acid. Quite quickly, a white powder began to form inside the reaction
mass. I began to heat the mixture in a water bath, at about 55°C the powder dissolved, it seemed as if ETH had decomposed, although some kind of
"oil" was visible floating in the reaction mass. I sat down for 15 minutes of heating at 50-52°C, I poured the nitro mixture into 700 ml of ice
water. A fine white precipitate fell out, but in a very small amount. 700 ml of water is only slightly cloudy.
Perhaps I warmed too little, only 15 minutes, instead of 30-45 minutes. Or I used insufficiently strong nitric acid.
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Do not heat the mixture. Erythritol reeterification goes well at room temperature, unlike pentaerythritol. I prepared ETN in this way.
| Quote: Originally posted by DennyDevHE77 | [rquote=685763&tid=159724&
Then I had 70g of PETN left, I made two liters of 1% sodium bicarbonate solution and began to heat PETN in it, when the solution boiled, a huge amount
of foam floated to the surface. After an hour and a half of boiling and regular stirring, the foam was gone, I filtered out PETN, and it turned out
that 42g of it remained.
What else could it be but sulfates that were destroyed during the boiling process? PETN can be contaminated, in addition to them, by under-nitrated
molecules, BUT, mono- and di-nitrates are soluble in water, trinitrate (PETRIN) is generally liquid. So besides sulfates, there could hardly be
anything. A little later, I suggested that perhaps PETN was simply hydrolyzed during boiling. But then taking 100 g of purified PETN obtained at WFNA,
and boiling them for an hour and a half in 2.5 liters of 1% soda solution, I filtered out 98 g of PETN. And maybe I lost them on the filter.
[Edited on 16-7-2023 by DennyDevHE77] |
Very strange. Did you check the water after boiling with Ba(NO3)2?
And how did you besiege PETN from acetone solution? Did you dilute hot acetone with hot water then cooled or you cooled acetone then washed with
water?
[Edited on 16-7-2023 by Etanol]
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DennyDevHE77
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What does it mean if I tested the water? Well, except that I checked it with indicator paper, as expected there was a slightly alkaline reaction. And
I boiled with sodium bicarbonate, I don’t really understand what barium nitrate has to do with it.
And I plant PETN whenever, sometimes I pour it in a thin stream into a large volume of ice water (if small crystals are needed), or I drop water from
a dropper (about 30 ml / min) to get larger crystals (they do not dust, do not stick to surfaces and much better compressible), usually 340 ml of a
solution of PETH in acetone requires 600 ml of water for complete precipitation of PETH. I pour a little more.
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DennyDevHE77
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| Quote: Originally posted by Tsjerk | | Quote: Originally posted by DennyDevHE77 |
What else could it be but sulfates that were destroyed during the boiling process? PETN can be contaminated, in addition to them, by under-nitrated
molecules, BUT, mono- and di-nitrates are soluble in water, trinitrate (PETRIN) is generally liquid
[Edited on 16-7-2023 by DennyDevHE77] |
Do you mean to say there can't be under nitrated PE in your PETN because you crashed the PETN in water? I think they are just not that soluble, so
they crash out together with the PETN and afterwards when you boil in such a large volume of water they do dissolve. No need for sulfate ester
hypothesis, just some not fully nitrated PE.
Did you do any cleanup besides crashing the nitration mixture in water or do you just assume that the initial crude product had to be pure and when it
wasn't it had to be sulfates? |
I do not build any hypotheses on sulfates and nitrate-sulfates. All this can be read in the specialized literature. Especially in the one that is
devoted to the outdated method of obtaining PETN (two-stage).
Regarding cleaning.
Before boiling in water, I wash the raw PETN with three 12-liter buckets of water. I pour the acid mixture into the first bucket, then rinse with cold
water from the second bucket, and then with hot water from the third.
Previously, well, actually, I always cleaned the heating element by boiling in acetone with the addition of sodium bicarbonate or ammonium carbonate
(but it is worse).
If the under-nitrated molecules of pentaerythritol would simply dissolve in water when boiled, then there would be no thick foam, which then
disappears. But in any case, I am sure that they are removed even when washing with hot water. 12l of water per 100-150g PETN is a lot.
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Etanol
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If PETN contained sulfoesters, then the water after boiling will contain H2SO4 and Na2SO4.
Na2SO4+Ba(NO3)2=>BaSO4 + 2NaNO3
You can find % sulfoesters in PETN.
[Edited on 17-7-2023 by Etanol]
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Hey Buddy
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| Quote: Originally posted by DennyDevHE77 |
Please tell me your method. I tried to implement the same method just last night. I took 10g of erythritol, and added them to 50g (27g) of sulfuric
acid (at room temperature), after 15 minutes, when the erythritol was almost completely dissolved, I poured this solution into 75 ml of 70% nitric
acid (extra pure for analysis) with the addition of 30 ml of conc. sulfuric acid. Quite quickly, a white powder began to form inside the reaction
mass. I began to heat the mixture in a water bath, at about 55°C the powder dissolved, it seemed as if ETH had decomposed, although some kind of
"oil" was visible floating in the reaction mass. I sat down for 15 minutes of heating at 50-52°C, I poured the nitro mixture into 700 ml of ice
water. A fine white precipitate fell out, but in a very small amount. 700 ml of water is only slightly cloudy.
Perhaps I warmed too little, only 15 minutes, instead of 30-45 minutes. Or I used insufficiently strong nitric acid.
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I have used a chilled H2SO4 bath to dissolve erythritol to reduce exotherm on HNO3 addition. It works, but I can't remember any distinct advantage. It
was cooled during that time and the reaction was fairly low temp. I'm a bit risky with energetics, and I can understand risky experimentation, but i
dont think I would heat a nitro derivative of erythritol to even 50 C unless it was remote without physical presence around reaction. The thermal DDT
mechanism of ETN is still not well understood, but lower nitrates are even less known. Just know there is risk there. For example, if someone wrote
about this procedure and it resulted in a DDT to full detonation in the lab, I would not be at all confused about what was responsible, because there
were mixed erythritol nitrate esters being heated together in an oxidizing mixed acid. Seems high risk/low reward. I think I bought erythritol
recently for around $4/lb in bulk.
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littlesky
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Registered: 12-6-2023
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Methods: Stir at room temperature, dissolve 10g Erythrose in 50ml concentrated sulfuric acid, and obtain yellow solution. Afterwards, slowly pour the
aforementioned yellow solution into 20ml of fuming nitric acid in an ice water bath, and the yellow solution quickly turns into a white suspension.
After stirring for a few hours, pour this suspension into 250ml of crushed ice, filter, and wash with ice water to obtain ETN crude product.
If there is no fuming nitric acid, it can be synthesized by mixing industrial nitric acid (65-68%) and concentrated sulfuric acid, but the dosage
needs to be slightly calculated. I have been using this method to produce ETN. The yield is even higher than the method using fuming nitric acid in
the literature.
Temperature issue, do not heat it, it is very dangerous. In this method, when the final step is poured into ice, a high temperature will cause etn to
decompose and release NOx, resulting in a significant decrease in yield. Just don't exceed the room temperature.
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Sir_Gawain
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What is your yield from this process?
“Alchemy is trying to turn things yellow; chemistry is trying to avoid things turning yellow.” -Tom deP.
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PLSHY
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Registered: 30-7-2023
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In fact, someone in China has carefully studied the synthesis of etn. I will attach a piece of material from a Chinese amateur. You can use Google
Translate for reference. I used this material to produce etn, and at most one batch produced more than 750 grams of etn, and the yield is maintained
at more than 80%, which is very amazing, and the color is very white. The etn produced by this method still maintains a pure white color after a year,
and it is even ugly There are other colors inside, which means that the quality of etn is very good. And, it needs to be reminded that please use
acetone for recrystallization, even if etn is difficult to precipitate in acetone, such recrystallization is better than methanol recrystallization!
[Edited on 31-7-2023 by PLSHY]
Attachment: ETN (1.9MB)
This file has been downloaded 1296 times
[Edited on 31-7-2023 by PLSHY]
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