So, first of all, everyone knows that you can make dioxane with ethylene glycol and sulfuric acid as NurdRage exposed in video (https://www.youtube.com/watch?v=9Zzrn-61XAY). But where I live (Argentina) it is impossible to obtain sulfuric acid, i can make it myself, but
using it to then make dioxane does not convince me in the work involved. So I have tried to make Dioxane using another acid that is not strong but
somewhat dehydrating and accessible to me. Phosphoric acid. So I did it and here is what I found. The Yield is on Dioxane Azeotrope.
BEST EXPERIMENT:
In a simple distillation apparatus, I mix 200ml of commercial grade Ethyelene Glycol (which is actually quite good!) And 30ml of commercial grade 85%
phosphoric acid, with a stir bar and a HotPlate to put and distill, The distillate came over at a range of temperature between 80-120 degrees Celsius.
Distillation takes time, but it is not slow. I recommend not isolating the equipment with aluminum foil because it distills more ethylene glycol, just
let it work. I got a total of 200 ml of what I call First distillate (Yes ... Name everything: v) Okey to these I added 10 g of sodium bisulfate
monohydrate and fractionated the mixture. I collected 19 ml at a temperature below 87 degrees. 94 ml at 87 degrees and a residue of 97 ml wass in the
distillation flask. Yield of Dioxan Azeotrope is 53%.
NOTES
Here are some things i found experimentally.
_ Isolation of the apparatus to increase distillation rate is BAD, More Ethylene Glycol comes over.
_ More Phosphoric acid or less, is does not Improve yeild.
_ Adding 10ml of Water per 100ml of Fist Distilate helps a bit.
_ Big apparatus are detrimental to the reaction, as the distillation requires more temperature and these produces more Side-Products
OTHER EXPERIMENTS AND CHEMICAL NOTES
I tried using 50 ml of phosphoric acid and 200 ml of Ethylene Glycol Yield: 25,99%
Using 20 ml of phosphoric acid and 200 ml of ethylene glycol Yield 38,42%
200 ml Ethyelene Glycol 30 ml Phosphoric acid and Big aparatus (To heat the reaction to higer temps) Yield 24,86% with a lot of products boiling at T
below 87 Degrees in Fractionation
Ethylene Glycol was Tech Grade, i distill it found it was very pure ! with very little water.
Phosphoric acid was 85% Food Grade. Crystal clear.
Apparatus was all Glass with Ground glass joints.
Hope these Helps anyone
[Edited on 31-7-2018 by Chem Science]
[Edited on 31-7-2018 by Chem Science]XeonTheMGPony - 30-7-2018 at 17:51
Try using anhydrous Iron sulfate, this can be don in a continuous flow system (add more as it is reacted via addition funnel)Chem Science - 30-7-2018 at 18:06
Hey ! thanks for the Data Xeon TheMGPoney xD VSEPR_VOID - 30-7-2018 at 18:26
What about doing this on a larger scale by refluxing bisulfate or phosphoric acid with PEG? j_sum1 - 30-7-2018 at 18:42
I too have been playing with dioxane synthesis. I actually have less phosphoric acid than sulfuric. I have had ok results with using sodium
bisulfate and intend to pursue that route a bit further.
@Xeon
What is the rationale behind the iron sulfate? And why anhydrous? Is the aim to mop up the water as it is produced? How are you adding this with an
addition funnel?Chem Science - 30-7-2018 at 18:57
Well, it happens that Sodium Bisulfate is a lot more expensive than Phosphoric acid here. That was my motivation for doing these. I will give it a try
on the PEG and Phosphoric reaction at some time. stamasd - 31-7-2018 at 07:45
Food-grade ethylene glycol? Who would make that? EG is toxic and not to be used in food.Chem Science - 31-7-2018 at 08:24
O MY GOD ... Sorry for that, yeah i know it's toxic. I Changed it Thanks xDwg48 - 31-7-2018 at 09:40
I too have been playing with dioxane synthesis. I actually have less phosphoric acid than sulfuric. I have had ok results with using sodium
bisulfate and intend to pursue that route a bit further.
@Xeon
What is the rationale behind the iron sulfate? And why anhydrous? Is the aim to mop up the water as it is produced? How are you adding this with an
addition funnel?
it is the glycol you add as it is consumed via addition funnel, the iron sulfate is the catylest, Anhydrous is that what is specified in the paper in
the other Dioxane threads.
it is the glycol you add as it is consumed via addition funnel, the iron sulfate is the catylest, Anhydrous is that what is specified in the paper in
the other Dioxane threads.
it is the glycol you add as it is consumed via addition funnel, the iron sulfate is the catylest, Anhydrous
is that what is specified in the paper in the other Dioxane threads.
Attachment: Dioxane excerpt from Elderfield's Heterocyclic Compounds volume 6.pdf (3.1MB)
Thanks Xeon.
This is the ref. from that paper for the iron sulphate method: van alphen, Rec. trav, chim., 49, 1040 (1930)
I tried searching for it but found nothing relevant. Can anyone parse that reference in to a book or journal name and any additional information I may
need to find it. Thanks in advance.
Xeon TheMGPoney xD 