Fantasma4500
International Hazard
Posts: 1681
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline
Mood: dangerously practical
|
|
Extremely dangerous and inadvisable method for producing nitrite esters (Split from "Preparation of ionic nitrites")
i did a run where i used 100ish mL of HNO3 and maybe 15g copper, boiled down the solution a bit before reacting it with IPA + HCl, acquired about 25mL
IPN - a slight bit tainted with IPA, it appears the IPA can both be in the water phase but also gets pulled out into the IPN
the IPN formed quickly pulls the IPA out of solution and seperates
i need to scale this up with proper dripping mechanism
i have 1 reaction flask with HNO3 being dripped into it, 1 airpump going in to force the gasses through (and eventually clean apparatus, and avoid
suckback)
and then distillation bridge going to next flask to collect water, HNO3 and avoid suckback, then hose attachment comes out of this to bubble into NaOH
biggest challenge in this whole thing is keeping apparatus cold, getting the nitric acid and also having a working setup- dripping funnel, this can
maybe be discarded by using lower conc HNO3 and dumping copper in like that
you get your second crop of NO2 by decomposing Cu(NO3)2 at 220*C, this gives same amount of NO2 as the nitric acid reaction does
[Edited on 12-15-2024 by Texium]
|
|
|
clearly_not_atara
International Hazard
Posts: 2801
Registered: 3-11-2013
Member Is Offline
Mood: Big
|
|
How are you differentiating isopropyl nitrite from isopropyl nitrate?
|
|
|
BAV Chem
Harmless
Posts: 28
Registered: 9-5-2021
Location: In the middle of nowhere
Member Is Offline
Mood: Thoroughly confused
|
|
Quote: Originally posted by Antiswat  | i did a run where i used 100ish mL of HNO3 and maybe 15g copper, boiled down the solution a bit before reacting it with IPA + HCl, acquired about 25mL
IPN - a slight bit tainted with IPA, it appears the IPA can both be in the water phase but also gets pulled out into the IPN
the IPN formed quickly pulls the IPA out of solution and seperates
i need to scale this up with proper dripping mechanism
i have 1 reaction flask with HNO3 being dripped into it, 1 airpump going in to force the gasses through (and eventually clean apparatus, and avoid
suckback)
and then distillation bridge going to next flask to collect water, HNO3 and avoid suckback, then hose attachment comes out of this to bubble into NaOH
|
Hey Antiswat, I can't quite follow this procedure here. I would think you added IPA and HCl to a solution of Cu(NO3)2 ...which
produced isopropyl nitrite? Now that seems like it wouldn't work.
Or did you just react IPA, HCl, HNO3 and Cu directly to afford a whole slew of reactions which end up producing isopropyl nitrite amongst
other things.
Either way this brings me to another idea which might just work to make nice and pure alkali nitrite.
I'm thinking if you react nitric acid with a large excess of EtOH you'll get a whole bunch of interesting reaction products: NOx gasses,
HNO2, Acetaldehyde, Acetic acid, CO2... and eventually Ethyl nitrite. The latter is a gas and could easily be bubbled through an
ethanolic solution of NaOH or KOH, affording the corresponding alkali nitrite which precipitates out.
I've already done some test with ethanol and nitric acid. If a large excess of EtOH is used the resulting gas is colorless and certainly smells like
Ethyl nitrite. It also burns with the characteristic white flame of nitrite esters.
Quite possibly one could even substitute nitric acid for a nitrate salt and a mineral acid.
What do you think about this approach?
[Edited on 20-6-2022 by BAV Chem]
|
|
|
Fantasma4500
International Hazard
Posts: 1681
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline
Mood: dangerously practical
|
|
the procedure was reacting Cu with HNO3 to form Cu(NO3)2 and NOx, was was pumped into NaOH to yield NaNO3/NaNO2- this solution was reduced and then
reacted with IPA/HCl to form IPN
i have thought of directly pumping it into IPN but it might give other compounds as well that you then have to deal with seperating, volatile ones,
potentially explosive.
HNO3 and EtOH? interesting. ascorbic acid also works despite the ascorbic acid reacts with the NOx
https://en.wikipedia.org/wiki/Calcium_nitrite
this would explain that NOx + hydroxide is indeed a quite viable method. burning dry ammonia is also an idea, but thats a more complicated apparatus,
imo. oh i might also stress... ethyl nitrate may derive from HNO3+ EtOH. methyl nitrate is a high-explosive with decent sensitivity. thiscould be a
dangerous reaction.
upon reading your writings on Etnitrite- thats very interesting... Etnitrite is like 13*C boiling point or something iirc, i would try this with IPA
where the resulting nitrite is boiling at about- hm 40*C? this is much easier to handle, less volatile, you will need to react this chemical with NaOH
to once again produce the desired nitrite salt.
NaHSO4 + nitrate could do yeah, though i think activating the NaHSO4 takes some heat- you might have to distill on it seperately first, thus arriving
at HNO3
cant platinum or something catalyse the decomposition of nitric acid? there has got to be some more simple way to this
i would indeed say the nitrite flame is quite likely .... buuut that could also be the same with nitrate? so acquire an amount of this material and
test boiling point maybe, i usually just put digital thermometer into a testtube and carefully heat it
maybe we should look further into the decomposition of HNO3? as i mentioned, Cu(NO3)2 - which can be made by Ca(NO3)2 + CuSO4 decomposes at 220*C to
yield decent amounts of NO2 as it turns into CuO. if some NO forms thats actually much better than NO2, maybe we wanna also look into turning NO2 into
NO? my last searches on this yielded not much
|
|
|
Fantasma4500
International Hazard
Posts: 1681
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline
Mood: dangerously practical
|
|
HNO3 --> isopropylnitrite!
i'd just like to report a pounding success. as im messing around with bulk dissolution of silver alloy in dilute nitric acid i showed off to one
non-chemist what nitric and copper can do, because its so toxic and beautiful, he had some acetone standing around and i added a bit into it, for
science- to see if anything interesting would happen. it died down and there was a vague organic nitrite scent, very mild vasodilatory effect, aha.
so i took a bit of copper wires, maybe 15% HNO3 and added about 1mL IPAlcohol to the.. 15mL mixture of acid
let it stand for maybe 3 hours roomtemperature, color changed very mildly due to copper metal dissolution
and, due to IPNitrite being very volatile i can indeed testify that theres a very strongly vasodilatory substance now in my 50mL erlenmeyer flask
so- simply scale this up, figure out how much % acid one can use, what temperature- preferably 50*C so you can immediatedly distill over the isopropyl
nitrite and right away react with sodium hydroxide to form our dear sodium nitrite in quite pure form
alternatively ethanol may be used, nitric acid and alcohol may cause a runoff and cause explosive formation thus its ideal to not increase the
temperature very much as for, distilling it out as its hard to tell what could set off organic explosives in a glass vessel, perhaps some solvent
could be used to extract the nitrites, but that would also risk carrying over an organic nitrate, which would then contaminate the nitrite
its plausible we can go as low tech as HCl + KNO3 + Cu + IPAlcohol --> IPNitrite + NaOH --> NaNO2 + IPAlcohol
update: i mixed 30mL mL IPA with 30mL 62% HNO3, and 90mL H2O, giving 120mL 15% HNO3
at room temperature this caused a slight runoff but clearly giving off some vasodilatory fumes, more dilution or controlling temperature better might
be the way to go, seems to work without copper, albeit more difficult to control
[Edited on 13-8-2023 by Fantasma4500]
|
|
|
clearly_not_atara
International Hazard
Posts: 2801
Registered: 3-11-2013
Member Is Offline
Mood: Big
|
|
You inhaled crude isopropyl nitrite?!
Well, I guess we know it works...
|
|
|
Fantasma4500
International Hazard
Posts: 1681
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline
Mood: dangerously practical
|
|
well, i tasted sodium cyanide too, bitter taste stuck 30 mins, tongue numb 2 weeks
chloroform, tastes nice and sweet
accidentally inhaled HF while doing silversolderings, strongly acidic smell, and boron trifluoride
dived into a thick fog of SO3
walked through a fog of Cu/CuO
tremors from nickel poisoning
acquired a diabolic headache lasting hours by taking a single drop of 10% EGDN in acetone and placing on my arm
a slight vasodilation from IPNitrite is not something to worry about.
|
|
|
Alkoholvergiftung
Hazard to Others
Posts: 190
Registered: 12-7-2018
Member Is Offline
|
|
I hope you never try this methode on mercury compounds.
|
|
|
Master Triangle
Harmless
Posts: 19
Registered: 24-12-2013
Member Is Offline
Mood: No Mood
|
|
| Quote: Originally posted by Fantasma4500 | | i hope the general community will maybe in 2025 be able to grasp the simplicity and blessing that this method, as brought to us by woelen from an
ancient chemistry book is, a forgotten gem and a true blessing in current times where nitrites are scarce due to it offering an easy way out of life
|
I very much hope so too, and am working tower some part of it!
Can't recall what their reference was, but I know some of the early methods of producing alkyl nitrites used nitric acid and sulfuric acid with copper
turnings, which would react with the chosen alcohol to produce the nitrite. Ref is Organic Medical Chemicals by M. Barrcliff and Francis H. Carr. I
presume this made nitrous acid in-situ, and hopefully dominated over nitration since they didn't make any recommendations on how to not die from
distilling ethyl nitrate, but who knows with books that old.
Also, I keep getting "form not secure" notifications and can't post anything unless I have logged out and logged back in for every post. Anyone know
what that is?
|
|
|
jackchem2001
Hazard to Self
Posts: 53
Registered: 2-6-2024
Member Is Offline
|
|
An oxidizing agent is one which can accept a lone pair and eliminate an adjacent proton. Nitric acid acts as an oxidizing agent on alcohols - it
accepts a lone pair to become nitrous acid and gives the carbonyl. Hence (ignoring acid concentration effects - see later in the post) with one
equivalent of nitric acid two equivalents of alcohol ought to be used (to give 1 equivalent of carbonyl and nitrite ester, with the latter being
easily seperated by distillation due to its volatility). Further reduction of nitrous acid is not said to occur (the product nitroxyl is unstable).
Boiling points of relevant compounds:
Acetone - 56°C
Isopropyl nitrite - 40°C
Diisopropyl ether - 69°C
Isopropyl nitrate - 102°C
Isopropyl alcohol - 82°C
Nitric acid - 83°C
Water - 100°C
This oxidiation reaction is quite violent and only seems to occur above a certain concentration of acid. The nitric acid may be accessed by sulfuric
acid and a nitrate salt, but if you add enough water to dissolve everything then the nitric acid concentration seems to be too low to affect
oxidation. Nitrogen dioxide evolution is seen and no external heat is needed to distill something from the mixture.
The reason I say something is because when I did this (using sulfuric acid, potassium nitrate, and isopropyl alcohol without any copper) I got a
yellow water immiscible liquid which matches isopropyl nitrite. However, the flame color was orange not white, and its boiling point was 54-58°C.
When the crude material was left in contact with water overnight, the boiling point rose to 72-74 degrees - which I might hope is diisopropyl ether
forming through SN1. I did not do any other tests with this procedure like fractionating the mixture.
To reiterate the stoichoimetry from earlier: if you draw a mechanism using sulfuric acid with one mol of nitrate salt, one 'proton mol' is needed (but
it might be best to use more acid to give the needed concentration for oxidation) and two mols of water are produced. Two mols of alcohol are needed,
giving one mol of carbonyl and one mol of nitrite ester. I think it would also make sense to add the isopropyl alcohol dropwise to the acid mixture
and not the other way around.
[Edited on 20-7-2024 by jackchem2001]
|
|
|
BAV Chem
Harmless
Posts: 28
Registered: 9-5-2021
Location: In the middle of nowhere
Member Is Offline
Mood: Thoroughly confused
|
|
| Quote: Originally posted by Master Triangle |
Can't recall what their reference was, but I know some of the early methods of producing alkyl nitrites used nitric acid and sulfuric acid with copper
turnings, which would react with the chosen alcohol to produce the nitrite. Ref is Organic Medical Chemicals by M. Barrcliff and Francis H. Carr. I
presume this made nitrous acid in-situ, and hopefully dominated over nitration since they didn't make any recommendations on how to not die from
distilling ethyl nitrate, but who knows with books that old. |
I tried a similar method of making isopropyl nitrite earlier this year with hydrochloric acid and sodium nitrate instead of sulfuric and nitric acids
as those are quite valuable to me. The reaction seems to work quite well at first but after a while it only produces NO instead of the alkyl nitrite.
I think this is because after a while water from the HCl starts to build up in the reaction and that leads to side reactions producing NO. In the end
I never got yields better than 20% but I might try again at some point with NaHSO4 instead of HCl. I also tried a small scale test with
oxalic acid instead of HCl and that did afford quite a bit of isopropyl nitrite but sadly I screwed up later on and lost everything from that run so I
don't know about the yield.
Interestingly this reaction isn't even all that dangerous. Yeah it likes to run away in the beginning with HCl but other than that it seems to run
along just fine. The isopropyl nitrite always distilled over nicely without decomposing.
Btw i also got a message saying this web form is not secure when i was trying to log in yesterday. Turns out I was on
https://www.sciencemadness.org/talk/misc.php?action=login and changing it to https://www.sciencemadness.org/whisper/misc.php?action=login did the trick.
|
|
|
Master Triangle
Harmless
Posts: 19
Registered: 24-12-2013
Member Is Offline
Mood: No Mood
|
|
The source I was reading did use surprisingly little water, so little that I thought they would produce some alkyl nitrates, but I am not familiar
with nitrations, maybe that little bit of water was enough to prevent it.
It could be the HCl though, wikiped says HCl can reduce NO2 to nitrosyl chloride, although I thought that would react with alcohols to produce the
nitrite anyway (and HCl) in much the same way as nitrosylsulfuric acid. Also, did two layers form? If there is a low concentration of alcohol in the
aqueous layer I guess that could lead to NO escaping before the nitrous acid can react with the alcohol, but the production of nitrite certainly
shouldn't stop.
Interesting that it might work with oxalic, since copper oxalate is super insoluble. Did it consume the copper, or did it bubble? I kinda wonder if
the nitrate just allows the copper oxalate to dissolve or if the oxalate could actually be the main reductant there. Either way it could be a superior
synth, was that just with nitrate salt too?
I'll try the alkyl nitrite to nitrite salt reaction once I have enough nitrites, I really want to see if it is efficient within a practical timeframe
(sounds like it takes ages), still continuing with the aluminium reduction but getting the salt with a method that uses an alkyl nitrite intermediate
might lead to a very pure product free of nitrates and other salts if you can get the NaOH out.
|
|
|
BAV Chem
Harmless
Posts: 28
Registered: 9-5-2021
Location: In the middle of nowhere
Member Is Offline
Mood: Thoroughly confused
|
|
As far as I know the copper itself acts as the reducing agent in this reaction.
The HCl liberated nitric acid from the nitrate salt, that's for sure:
NaNO3 + HCl ---> NaCl + HNO3
This should have then reacted with the copper giving copper nitrate, water and nitrous acid:
Cu + 3 HNO3 ---> Cu(NO3)2 + H2O + HNO2
The latter would of course react with the alcohol, forming a nitrite ester:
ROH + HNO2 ---> RNO2 + H2O
With excess HCl more nitric acid should be generated from the copper nitrate:
Cu(NO3)2 + HCl ---> CuCl2 + HNO3
Now the actual chemistry happening in solution is probably a lot more complicated and involves a few more reactions.
I also got this process from Organic Medical Chemicals by Barcliff and Carr. The amounts of reagents were roughly equivalent to their method with a
bit of tweaking to match the new stoichiometry a little better. I wrote some of this stuff down so I can roughly tell you what I was doing there.
Trial 1) HCl:
10g NaNO3
55ml HCl (~23%)
100ml iPrOH
10g Cu (finely cut wire)
These reactions were carried out near the boiling point of the alcohol, so the nitrite would boil right out. It briefly acted up a little at the
start, producing some NO2 fumes but then calmed back down. Over time two layers formed, a light green layer of alcohol on top and a nearly
black layer of salt solution beneath it. There was some bubbling coming from the copper and I assume that was NO gas arising from side reactions like
2 HNO2 ---> H2O + NO2 + NO
which i guess could have happened in the bottom layer where there wasn't a lot of alcohol to react with the nitrous acid. Iirc the production of
nitrite ester never really stopped but just got really slow and inefficient at some point.
Trial 2) Oxalic acid:
10g NaNO3
25g oxalic acid
20ml HCl (~23%; added later)
100ml iPrOH
10g Cu (finely cut wire)
Same reaction conditions as before. This time it didn't run away but was a bit slower than the other run. Interestingly the oxalate doesn't seem to
act as a reducing agent itself, it just displaces the nitrate ions from their salts and ends up precipitating copper oxalate, which is just as
insoluble as you'd expect it to be. No layer separation occured this time. At some point I added some HCl to hopefully liberate more HNO3
and also because I found an error in my calculations but that didn't really do much (if memory serves).
In both cases quite a bit of the copper dissolved, especially with HCl because a lot of copper(I) chloride formed as well. Anyways the reaction is a
low yielding mess with HCl with all the side reactions you get.
|
|
|
bnull
Hazard to Others
Posts: 488
Registered: 15-1-2024
Location: South of the border, wherever the border is.
Member Is Offline
Mood: Happy New Year!
|
|
Organic Medicinal Chemicals, by Barrowcliff and Carr (https://archive.org/details/organicmedicinal00barruoft).
Quod scripsi, scripsi.
B. N. Ull
P.S.: Did you know that we have a Library?
|
|
|
Texium
Administrator
Posts: 4622
Registered: 11-1-2014
Location: Salt Lake City
Member Is Offline
Mood: PhD candidate!
|
|
Y'all- it's time to take a break and recognize the very real hazards that arise when improvising with mixing alcohols and nitrating mixtures. Test
tube scale is one thing, but trying to adapt this chemistry for production of nitrites is a disaster waiting to happen. See here: https://www.sciencemadness.org/whisper/viewthread.php?tid=16...
It comes as little surprise to me that this absolute bonehead procedure originated with Fantasma/Antiswat. Clearly a pinnacle of great judgement:
| Quote: Originally posted by Fantasma4500 | well, i tasted sodium cyanide too, bitter taste stuck 30 mins, tongue numb 2 weeks
chloroform, tastes nice and sweet
accidentally inhaled HF while doing silversolderings, strongly acidic smell, and boron trifluoride
dived into a thick fog of SO3
walked through a fog of Cu/CuO
tremors from nickel poisoning
acquired a diabolic headache lasting hours by taking a single drop of 10% EGDN in acetone and placing on my arm |
Advice for others: make sure to do more thorough research before attempting a procedure suggested by someone with so little regard
for their personal well-being.
As addressed in the linked thread, isopropanol will in part be oxidized to acetone under these conditions which will also react violently with nitric
acid. Copper is necessary to have in the reaction as a reductant to keep it from getting out of control. Replacing copper with excess isopropanol
works on paper, as it's the same number of electrons moving around, but in practice, it's setting you up for a runaway since isopropanol is a stronger
reductant and the acetone produced can also react. Even with copper, it's still a risky procedure that shouldn't be recklessly scaled up. Without
copper, it's suicidal. Using HCl in the mixture is also not a great idea. Now you're essentially making poor man's aqua regia and who knows what else.
HCl can not substitute for H2SO4 without altering the chemistry that's occurring significantly.
A good rule of thumb for scaling up reactions is no more than 3x the scale of what you previously carried out.
I'm putting this thread in Responsible Practices. Please stick to safety discussion here. If you want to write up a well-referenced procedure that
clearly covers the safety risks, start a new thread. I don't think blending it into the big ionic nitrites thread is a great idea since the discussion
gets broken up by all the discussion of inorganic methods and details get lost along the way.
|
|
|
Texium
|
Thread Moved
15-12-2024 at 10:53 |
jackchem2001
Hazard to Self
Posts: 53
Registered: 2-6-2024
Member Is Offline
|
|
Thanks for doing that. This is probably where the idea originated from: https://www.sciencemadness.org/whisper/viewthread.php?tid=52...
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
