MöbiusMan
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Synthesising 1,4 Dioxane
Ok, I finally did it.
I somewhat followed NurdRage’s video and Dough's but have come up with a better one.
First distill your antifreeze and collect the pure ethylene glycol; it boils at about 200ºC so i used an air condenser with a wet towel placed over
it as water jacket condensers may crack due to thermal stress. Once you finish distilling the ethylene glycol, you will see a bunch of salt and
corrosion inhibitors left in the flask and can wash them out with water.
You also want to distill your sulfuric acid if you are using drain cleaner; Use pieces of terracotta pot as boiling chips, they will react at first
and colour the acid red but then stop reacting and make perfect boiling chips, NO BUMPING AT ALL. Once that was distilled, depending on the brand you
may have some junk left in the flask.
Now put however much ethylene glycol you have in a large jointed flask. You want to have a lot of headspace in you flask as it will foam up a lot (I
used a 2L flask for 500ml of ethylene glycol). Then add 7% of the volume of ethylene glycol of your 98% sulfuric acid. Set up a fractional
distillation with a vigreux column or others and heat up your mixture; use strong stirring. Collect everything that comes over and continue heating
the reaction flask. Towards the end of the distillation the reaction flask will turn a dark brown and eventually a tarry black. It is important to
keep strong stirring all the way through to stop the foaming. It is at this point most people's yield goes out the window because they stop too early
due to the foam. This is why we use the oversize flask. Continue heating until the foam is super thick and fills the flask. You need good ventilation
as a lot of vapours form and are toxic. Turn off heating before it all overflows and save your distillate from the oncoming foam if necessary.
I collected about 400 - 450ml of crude distillate from 500ml of ethylene glycol. To this distillate I add 5% of the distillates volume in 98% sulfuric
acid. Set up another fractional distillation. Heat the flask and you will collect a bunch of impurities which boil at about 40 - 50ºC. When the still
head reaches 86ºC change out the receiving flask and collect your dioxane. The temperature should then sit at 87.7ºC for a while and the rate of
distillation will greatly increase. Continue collecting until 93ºC at which point the distillation is over.
With this purified dioxane, add NaCl with strong stirring and intermittently stop stirring and wait a minute. If no by-phase has formed continue
adding NaCl. Continue doing this until you have a nice by-phase with a little extra pile of salt at the bottom. I left mine to stir for an hour on
strong stirring.Then pour the mixture into a separatory funnel. Allow the layers to separate and drain away the lower aqueous layer. Collect your
upper dioxane layer in another flask.
To this dioxane add some NaOH using the same method mentioned before (stirring then waiting for a by-phase to form). This time, make sure there is a
decent amount excess NaOH sitting at the bottom. Stir this for another couple of hours. It will turn an orange colour and you may have solid bits of
polymerised impurities. If you do it right the lower layer should form a semisolid thick gel layer. Add the mixture to a clean separatory funnel and
allow the layers to settle. Drain away the lower orange/red layer, and collect the upper dioxane layer.
Using sodium magnesium aggregate further dry the dioxane with stirring overnight; make sure to not seal it as pressure may build up. Then distill the
dioxane using a simple distillation and collect whatever boils at 100-103ºC. If there wasn't much water you may be able to create sodium spheres as
you distill it but most of the time you won’t get much at all. The second time you distill the dioxane with sodium magnesium aggregate you will get
alot more sodium as the dioxane is now completely dry.
Its amazing how much you can write when you enjoy what you write about.
If you have any questions write them in below.
Good Luck and Happy Carcinogening!
[Edited on 15-7-2018 by MöbiusMan]
If chemistry was easy it would be called biology.
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j_sum1
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Thanks MM.
I have been doing the same thing the past couple of days. Again following Nurdrage pretty explicitly.
Batch 1 was about 300mL of antifreeze in a 500mL RBF using 40mL of sulfuric acid. I managed to have it foam over twice and so it got triple
distilled. Then 10mL of Sulfuric acid added to the distillate and fractional distillation. Product looked clean and clear at this stage. This was
followed by stirring with NaOH for several hours. I got some dark waxy-looking lumps appear quite quickly and two liquid layers. The organic layer was
still very amber in colour so I responded with a large amount of additional sodium hydroxide. The result was an orange sludge of polymer gunk and a
much smaller amount of discoloured dioxane. I filtered and have a measly 50mL that will still need distilling to purify.
Batch 2 was 250mL usung 60g of sodium bisulfate. Distillation was a bit slower but not unreasonably so. Distillate came over with a yellow tinge
before foaming occurred so the process was halted. Volume yield seems ok at this point but I have not cleaned it up yet. Tarry mess with solidified
NaHSO4 looked a real mess to clean at first. But adding some NaOH and a bit of water and leaving it over night loosened it up nicely. Washing it out
left a lovely sparkling flask.
I will try the NaCl salting out. That might be a step in the right direction following my hydroxide mess.
If, as you say, the sodium synthesis needs very dry dioxane, it might be better to distil over NaOH rather than just stir and decant.
I will be doing a few runs over the next couple of weeks so I can play with the parameters a little.
[Edited on 15-7-2018 by j_sum1]
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MöbiusMan
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Yes, the NaCl salting will remove most of the water so you save on sodium hydroxide and it forms less wastage in the gelatinous stuff. What yield of
distillate did you get on the first distillate because I found a lot of the distillate comes over when the foaming gets intense. This could be a one
of the reasons people get such a low yield for this synthesis. Having a massive flask to allow the foam to build was the way i handled it.
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j_sum1
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I did not measure reagents accurately so don't know the yield.
I am limited to a 500mL rbf for heating. There was quite a bit of liquid there when it began foaming. Hard to estimate volume of a foam but I would
reckon equivalent of 80-100 mL of reagent from a ~300mL charge.
Maybe one of the secrets is not to be too ambitious with batch size since it will be lost anyway.
Or maybe it is worth putting an addition funnel into the process.
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XeonTheMGPony
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I'm going to give the iron sulfate method a go, I just made some from 23grams of iron turnings, it is now a nice pale green crystal structure filling
the bottom of the beaker, need to dry this to anhydrous state
Attachment: 1,4-Dioxane msds.pdf (456kB)
This file has been downloaded 347 times
Attachment: Dioxane excerpt from Elderfield's Heterocyclic Compounds volume 6.pdf (3.1MB)
This file has been downloaded 366 times
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j_sum1
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Thanks for that Xeon. I haven't read the whole thing but it is fascinating thus far. Separation of Li from other group I salts. Whodathunkit?
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XeonTheMGPony
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Quote: Originally posted by j_sum1  | | Thanks for that Xeon. I haven't read the whole thing but it is fascinating thus far. Separation of Li from other group I salts. Whodathunkit?
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http://www.sciencemadness.org/talk/viewthread.php?tid=65311
Credit belongs to this thread! We should have a Dioxane sticky
As I suspect a great many threads will be popping up!
I'll add some pictures of my iron sulfate and eventually dioxane work up to one of these threads, probably the larger one.
I plan to use my addition funnel (250ml) and a 500ml 3 necked flask to try and do a continuous flow system
Just a tip to you guys, Seafoam containers will be ideally suited to storing Dioxane as they are a stamped aluminium seamless bottle with a fairly
good sealing cap on them, and around here at least you find them around the roads due to ignorant people littering, so keep an eye out!
I use them to store my used alcohol for drying, I then dry/distill and use it in my alcohol burner.
[Edited on 15-7-2018 by XeonTheMGPony]
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MöbiusMan
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I got up early this morning at 5:30 and went up to the lab to check on things and found that my distance has frozen. Guess that's expected seen as it
was 3 degrees C. Well that gives me some confidence that I actually have dioxane. Bloody climate change its nearly sub zero in Sydney! Grrrrr
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Vosoryx
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I used is 11 Celsius melting point to crystalize it before I used it in my sodium synthesis, just by heating the flask it was in and then placing it
in a closed thermos in the fridge. At the end there was a tiny bit of water that I couldn't even pour off - I had to put a cool paper towel on it to
remove the water.
It wasn't needed though, the Na/MgO would have removed it. I just wanted a crystal because it was my science fair project and I wanted it to look cool
on the poster board. Of course, it didn't even produce a crystal, just solidified inside the flask in the thermos.
"Open your mind son, before someone opens it for you." - Dr. Walter Bishop
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MöbiusMan
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This raises the question if it is possible to purify dioxane by recrystallisation
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Vosoryx
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Experiments will have to be done. 
I'll add it to my growing list of things to do.
"Open your mind son, before someone opens it for you." - Dr. Walter Bishop
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MöbiusMan
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Wohooooo
I have sodium. The dioxane i made must be good because this is what i got. I didn't have any isopropyl on hand to coaless the sodium and found that
adding a few drops of the dioxane worked out and I ended up with a nice chunk of sodium. It even has those crystallisation lines that NurdRage talked
about in his vid. Yieeewwww
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Boffis
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Nice work MobiusMan!
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MöbiusMan
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Heheheheh I've been back in the lab. I'm addicted to the joy you get when you see those silver beauties forming.
If chemistry was easy it would be called biology.
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monolithic
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I filled a 1000 ml round bottom flask, set up for simple distillation, with 350 ml of purified ethylene glycol. I then added 35 ml 93% w/w H2SO4 in
one portion. Heating and stirring were applied. Distillate came over at 120 C, tapering down to 105 C at the end, where foaming became too intense to
continue. I haven't proceeded with the rest of the reaction so I'm not sure of yield just yet.
Videos on YouTube show distillations between 90-100 C when the H2SO4 is added to the ethylene glycol. Why is this -- why are my still head
temperatures so high? Ethylene glycol boils at 197 C so it can't be unreacted ethylene glycol coming over.
[Edited on 5-23-2020 by monolithic]
[Edited on 5-23-2020 by monolithic]
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draculic acid69
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| Quote: Originally posted by j_sum1 | I did not measure reagents accurately so don't know the yield.
I am limited to a 500mL rbf for heating. There was quite a bit of liquid there when it began foaming. Hard to estimate volume of a foam but I would
reckon equivalent of 80-100 mL of reagent from a ~300mL charge.
Maybe one of the secrets is not to be too ambitious with batch size since it will be lost anyway.
Or maybe it is worth putting an addition funnel into the process. |
Do u mean as a bulb between the neck of the flask and the distillation head?
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draculic acid69
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Also just found this:https://m.youtube.com/watch?v=0OhWEDtIQ2M
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monolithic
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As a follow up to my last post, I tried fractionally distilling the ethylene glycol + H2SO4. This brought the distillation temperature down a bit but
it was still fairly high. In total,
350 ml ethylene glycol + 35 ml 93% H2SO4, stirred 20 mins, simply distilled to yield 349 g crude distillate.
Added 35 ml 93% H2SO4 to distillate, stirred 20 mins, fractionally distilled to collect 87 - 95 C fraction total mass 205 g.
350 ml ethylene glycol + 35 ml 93% H2SO4, stirred 20 mins, fractionally distilled to yield 360 g crude distillate.
Added 35 ml 93% H2SO4 to distillate, stirred 20 mins, fractionally distilled to collect 87 - 95 C fraction total mass 211 g.
Combined both fractions, 416 g with total volume ~400 ml, and added 70 g KOH. Stirred between 1.0 and 1.5 hours.
Physical appearance: some black sludgy solids, lighter clear aqueous layer on bottom, dirty brown-red organic layer on top.
Discarded bottom aqueous layer, ~100 ml, as well as polymerized sludge.
Added another 25 g KOH, stirred for 1.5 hours. Majority of KOH did not dissolve as water was absent.
Physical appearance: undissolved KOH had some sludge on it, no aqueous layer, organic layer deeper brown-red color.
Gravity filtered solution and fractionally distilled to collect fraction 97.5 C - 102.7 C, crystal clear in appearance.
Total yield 272 g with a measured density of 1.02 g/ml @ 25 C (lit. 1.034 g/ml @ 25 C.)
Stored in an amber glass bottle with ~0.05 g BHT (~200 ppm) over 27 g activated 4A sieves (~10% w/w.)
Cleanup of the black sludge from the ethylene glycol + H2SO4 distillation was kind of shitty. Lots of acetone swirling and the stir bar had to be
scraped clean with a razor blade.
[Edited on 5-24-2020 by monolithic]
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ErgoloidMesylate
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| Quote: Originally posted by monolithic | As a follow up to my last post, I tried fractionally distilling the ethylene glycol + H2SO4. This brought the distillation temperature down a bit but
it was still fairly high. In total,
350 ml ethylene glycol + 35 ml 93% H2SO4, stirred 20 mins, simply distilled to yield 349 g crude distillate.
Added 35 ml 93% H2SO4 to distillate, stirred 20 mins, fractionally distilled to collect 87 - 95 C fraction total mass 205 g.
350 ml ethylene glycol + 35 ml 93% H2SO4, stirred 20 mins, fractionally distilled to yield 360 g crude distillate.
Added 35 ml 93% H2SO4 to distillate, stirred 20 mins, fractionally distilled to collect 87 - 95 C fraction total mass 211 g.
Combined both fractions, 416 g with total volume ~400 ml, and added 70 g KOH. Stirred between 1.0 and 1.5 hours.
Physical appearance: some black sludgy solids, lighter clear aqueous layer on bottom, dirty brown-red organic layer on top.
Discarded bottom aqueous layer, ~100 ml, as well as polymerized sludge.
Added another 25 g KOH, stirred for 1.5 hours. Majority of KOH did not dissolve as water was absent.
Physical appearance: undissolved KOH had some sludge on it, no aqueous layer, organic layer deeper brown-red color.
Gravity filtered solution and fractionally distilled to collect fraction 97.5 C - 102.7 C, crystal clear in appearance.
Total yield 272 g with a measured density of 1.02 g/ml @ 25 C (lit. 1.034 g/ml @ 25 C.)
Stored in an amber glass bottle with ~0.05 g BHT (~200 ppm) over 27 g activated 4A sieves (~10% w/w.)
Cleanup of the black sludge from the ethylene glycol + H2SO4 distillation was kind of shitty. Lots of acetone swirling and the stir bar had to be
scraped clean with a razor blade.
[Edited on 5-24-2020 by monolithic] |
Good to see a small cyclic ether can be made quite easily.
Cannula transfer and cannula filtering is used for lysergic synth Compressed air and remove co2
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B(a)P
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I am in need of some 1,4-dioxane for an an experiment that I intend to do once I have sourced the required regents and solvents. I intend to make the
1,4-dioxane via dehydration of ethylene glycol with sulfuric acid. I recently purchased some impure ethylene glycol (anti freeze) for this purpose.
What I have unfortunately realised since purchasing the ethylene glycol is that it is 50% water.
Is it worth distilling the ethylene glycol to remove the water before I attempt the dehydration reaction with sulfuric acid?
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j_sum1
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I would.
That said, I have never been very successful at dioxane synthesis. I have used ~100% ethylene glycol and also the same stuff pre-distilled. I think
I have lost a lot in the work-up with NaOH or KOH and made a lot of tarry goop. Which is to say, my advice might not count for a whole lot.
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B(a)P
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Thanks, I have never tried the synthesis, so any advice is most welcome. I was concerned my crude product would be too dilute and the dioxane I
produced would get mostly lost when I was trying to pull the water out. I will get rid of the water first.
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Fery
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Certainly remove the water as much as you can. During the reaction use only less of the catalyst, not 10%. 4% was enough in my case. You can add fresh
ethylene glycol then and repeat few cycles. Do not overfill the flask. Filling for only 1/3 is better than filling 1/2 of the flask.
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Texium
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Thread Moved
12-9-2023 at 11:48 |
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