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Author: Subject: Synthesising 1,4 Dioxane
MöbiusMan
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[*] posted on 15-7-2018 at 00:15
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]




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[*] posted on 15-7-2018 at 01:54


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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[*] posted on 15-7-2018 at 03:07


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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[*] posted on 15-7-2018 at 03:33


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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[*] posted on 15-7-2018 at 04:51


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



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[*] posted on 15-7-2018 at 05:11


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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[*] posted on 15-7-2018 at 05:32


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?


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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[*] posted on 15-7-2018 at 12:16


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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[*] posted on 15-7-2018 at 12:47


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.






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[*] posted on 15-7-2018 at 13:07


This raises the question if it is possible to purify dioxane by recrystallisation




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[*] posted on 15-7-2018 at 15:20


Experiments will have to be done. :)
I'll add it to my growing list of things to do.




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[*] posted on 17-7-2018 at 18:07


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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Screen Shot 2018-07-18 at 12.07.26 pm.png - 307kB




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[*] posted on 17-7-2018 at 22:43


Nice work MobiusMan!
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[*] posted on 18-7-2018 at 01:07


Heheheheh I've been back in the lab. I'm addicted to the joy you get when you see those silver beauties forming.

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