Also, the mechanism looks off to me, the structure on the right of the ether oxygen should have one extra carbon otherwise you would be making a 5 member ring
I have a hunch that keeping the glycol concentration low might minimize side products like tar and improve yields. Maybe dropwise addition into the hot acid, while the product is distilled off would be an improvement.
I think the problems appear when the concentration of sulfuric acid increases and E2 prevails over Sn2; maybe the continuous addition of ethylene glycol will help
My first thought was also that this reaction produces a lot of side products like polyethylene glycol, ethylene oxide and possibly even crown ethers. Lower concentrations may prevent this. But nice video, love to see more chemistry on youtube!
I admire the grit to make this. The hassle is enough to make me just want to purchase it. We use it quite often in my research lab, and I've learned that dioxane is quite hygroscopic. If you're intending to use it in a water sensitive reaction, it might be of benefit to you to store the solvent over 3 or 4 Å molecular sieves-and under nitrogen or argon, if possible.
Very interesting! You are on the way to become the next Nile Red? As a kid I had my own chemistry lab. Unfortunately I kept on poisoning myself due to a lack of proper training and safety environment. So I chose a different career path. After all them years poisoning the world with lead we finally see a shift to a new form of energy being used for transportation. Australia has become so lazy that they import distilled products like hydrocarbons for our vehicles.
Every time I see you throwing the stirrer bar into the flask under 90o angle I am afraid that the flask will break. Why don't you just let it slide down along the flask wall? Otherwise, it's a very informative video! Keep filming, please!
Nice. I never got around to making any before Nurdrage perfected the menthol catalyzed process. Having run that synthesis several times I'd say it might be nice to maximize yield by cleaning up with the dioxane, but I think I was getting 70% even with fairly old NaOH, and separation wasn't a huge hassle, though some tweaking with stirring speeds and other technique made a difference. The dioxane looked like magic though, can't wait to see how it goes.
Excellent video. Could you synthesize butyl diglyme sometime? One possible route would be to start with n-butanol react it with sodium hydride then let the resulting alkoxide react with ethylene oxide to form the aliphatic ether and the alcohol in the extreme carbon (this compound is also converted to alkoxide and then reacted with ethylene oxide). The resulting compound having the two aliphatic ethers and an alcohol group is let react with sodium hydride to form the alkoxide. The latter alkoxide is then reacted with an alkyl halide formed by reacting n-butanol with phosphorus pentachloride or hydrochloric acid in the presence of anhydrous zinc chloride (this alkyl halide is 1-chlorobutane). After all this steps the butyl diglyme is finally obtained. Two important ways of forming ethers in organic chemistry are used in this route. The opening of epoxides and the Williamson ether synthesis.
This TH-cam video having 301 videos for me reminds me of when YT API only allowed that number for new videos. In any case, I'm sure it's a great video, friend.
I don't have any experience in making PEG, though i am familiar with polymer chemistry. I have looked into it before, it seems like they often use polyethylene oxide which is added to ethylene glycol (or di/tri). Then depending on the desired molecular weight the catalyst is selected, where strong bases will result in low Mw polymers and more specialized organometallic catalysts can be used for more control and higher Mw synthesis. The problem i notice with products like PEG (and products that have existed for a long time) kind of lose the availability of knowing their production process simply by looking online. The production is obviously already perfected industrially but the information is just not publicly available (understandable but annoying), it's just very common with products like this! Usually i will look for papers that came out from 1900-1960 and see how it was first done, they can work but will never achieve the same quality as the perfected processes that companies have developed behind closed doors. To know how exactly these things are done today you need to know someone personally who can tell you (if not under NDA) or work in the industry urself.
@@Chemiolis yes. The ethylene oxide polymerization is very nasty I've been told. That's why any other method to make it would be interesting at least for small scales. But I guess the 6-membered dioxane is very favored compared to PEG. Perhaps this may work with longer dialcohols. Great videos!
It will react with water and dry the dioxane. I only did it because in the original vid he uses sodium, but i don’t think it’s really necessary. Drying it with sieves afterward is fine, and honestly putting a lot of effort to get super dry and pure dioxane is not really worth it unless u need it.
Upper. Dioxane has higher density than water so generally you’d expect it to be the bottom layer, but saturating the water layer with KOH significantly increases its density so it will be on the bottom.
Can u discuss more details? Such as type of side products, how H2SO4 will make the BP of impurities low, why NaOH cause the impurities to polymerize? And thanks for ur efforts in these awesome videos
Simple dehydration seems like a really dirty and polymerization-prone way to attack this synthesis. Perhaps there's a higher yielding way to attack the alcohols one at a time?
bake it in the oven at like 200C or so for an hour, generally NaOH has like 10% water if you bought it as drian cleaner and works fine for drying dioxane
@@EdwardTriesToScience thanks mate, I'll give that a try.. i think the sodium hydroxide I'm getting might be even wetter than 10%, i tried to make sodium metal and it completely failed and ate half way through the bottom of the flask so I've definitely got a water problem
@@markshort9098 Just melt it in nickel, silver or pure iron can. In the last one you may obtain slightly brown substance but I think it's not a huge problem
@@dimaminiailo3723 that was my first thought but the problem I see with melting it is it'll need to be smashed up after which would take a while and it would be absorbing water out of the atmosphere the whole time.. I need it dry for making sodium metal so I think I'll get some lithium out of a battery to dry it chemically, a little lithium contamination shouldn't cause to many problems
@@markshort9098 The cake surface is pretty small so it doesn't look to absorb as many water as it was initially. Just try it and work as fast as possible!
Very nicely done.. I just had an idea on why 1,4-Dioxane is considered to be carcinogenic. Isoelectronic with benzene was my thought. I don't understand Hückels rules well enough to confirm but I'm taking educated guess it substitutes for benzene.
@@bp8652 no he isn't he he takes time to make vids on his main channel just because chemiolis upload in a somewhat consistent manner doesn't mean that nilered doesn't do anything but I respect your opinion but to kill the time he upload shorts so we have something to watch but hey I get you
@@yasserotb1454 NileRed definitely puts a lot of effort in perfecting his content. The problem with a large project can also be that if you are halfway and it has completely gone wrong and u can't get it to work it will basically be useless and u wasted a lot of time. He also comes up with many methods himself these days which aren't easily laid out in papers, so it takes a lot of extra time. In a podcast i was listening he said he would stop focusing on main channel vids for now (he said he was tired of that style of content) and will focus on new style like shorts and NileBlue. (He said in patreon exclusive ep31 safety third podcast). Anyhow, i will just do whatever i feel like doing, but i don't have Nile's lab :'). Many things i just can't do (yet).
In your mechanism diagram, Diethylene glycol and the intermediates directly preceding and proceding it are all missing the 2nd carbon right of the central oxygen.
Also, the mechanism looks off to me, the structure on the right of the ether oxygen should have one extra carbon otherwise you would be making a 5 member ring
oopsie i made a small mistake while drawing this, it should indeed have one more carbon, but the essence of the mechanism stays the same!
The king of low yields is better than no yields. 😊 I think you're doing just fine. Another great episode!
Instead of a simple destillation it would be probably better to boil on reflux, so the reagents have more time to react.
I have a hunch that keeping the glycol concentration low might minimize side products like tar and improve yields. Maybe dropwise addition into the hot acid, while the product is distilled off would be an improvement.
I think the problems appear when the concentration of sulfuric acid increases and E2 prevails over Sn2; maybe the continuous addition of ethylene glycol will help
My first thought was also that this reaction produces a lot of side products like polyethylene glycol, ethylene oxide and possibly even crown ethers.
Lower concentrations may prevent this.
But nice video, love to see more chemistry on youtube!
I really appreciate how you include mechanisms! Keep up the good content!!
Same here! Seeing and recognizing some of the mechanisms helps my organic chemistry knowledge feel more practical and useful!
What a funky heating mantle, I love it
Thanks for posting this. I'm a retired chemist. It's fun to see.
I admire the grit to make this. The hassle is enough to make me just want to purchase it. We use it quite often in my research lab, and I've learned that dioxane is quite hygroscopic. If you're intending to use it in a water sensitive reaction, it might be of benefit to you to store the solvent over 3 or 4 Å molecular sieves-and under nitrogen or argon, if possible.
That's a cool looking heating mantle, is it an old style? I've never seen one like that before. Great video!
Very interesting! You are on the way to become the next Nile Red? As a kid I had my own chemistry lab. Unfortunately I kept on poisoning myself due to a lack of proper training and safety environment. So I chose a different career path. After all them years poisoning the world with lead we finally see a shift to a new form of energy being used for transportation. Australia has become so lazy that they import distilled products like hydrocarbons for our vehicles.
He does have early Nile Red vibes, like way back in the day before he started adding humour to his content, which both have their own advantages.
What did you poison yourself with? Old chemistry sets were the BEST!
Guessed it! I had a hunch that you’ll try nurdrage’s sodium metal procedure. Good luck! Looking forward to seeing it!
Neat video dioxane is a very interesting chemical. You really explain how to get rid of impurities etc and make a good product.
amazing video, gonna be nile red 2.0 in a couple years
Every time I see you throwing the stirrer bar into the flask under 90o angle I am afraid that the flask will break. Why don't you just let it slide down along the flask wall? Otherwise, it's a very informative video! Keep filming, please!
Really cool mechanism
Nice. I never got around to making any before Nurdrage perfected the menthol catalyzed process. Having run that synthesis several times I'd say it might be nice to maximize yield by cleaning up with the dioxane, but I think I was getting 70% even with fairly old NaOH, and separation wasn't a huge hassle, though some tweaking with stirring speeds and other technique made a difference. The dioxane looked like magic though, can't wait to see how it goes.
I would like to ask a question . Why only dioxane will be formed ? There must be crown ethers formed ? Can we make 18crown-6 by this
Refer to J.D lee and its further readings on crown ethers and their formations
Finally that one semester worth of reaction mechanism paid off
thanks Chemiolis. you are a genius . Please what kind of heating mantle are using? It looks like an aluminum one
Excellent video. Could you synthesize butyl diglyme sometime?
One possible route would be to start with n-butanol react it with sodium hydride then let the resulting alkoxide react with ethylene oxide to form the aliphatic ether and the alcohol in the extreme carbon (this compound is also converted to alkoxide and then reacted with ethylene oxide). The resulting compound having the two aliphatic ethers and an alcohol group is let react with sodium hydride to form the alkoxide.
The latter alkoxide is then reacted with an alkyl halide formed by reacting n-butanol with phosphorus pentachloride or hydrochloric acid in the presence of anhydrous zinc chloride (this alkyl halide is 1-chlorobutane).
After all this steps the butyl diglyme is finally obtained.
Two important ways of forming ethers in organic chemistry are used in this route. The opening of epoxides and the Williamson ether synthesis.
This TH-cam video having 301 videos for me reminds me of when YT API only allowed that number for new videos.
In any case, I'm sure it's a great video, friend.
Very interesting! Do you know of any conditions in which you could make polyethylene glycol?
I don't have any experience in making PEG, though i am familiar with polymer chemistry. I have looked into it before, it seems like they often use polyethylene oxide which is added to ethylene glycol (or di/tri). Then depending on the desired molecular weight the catalyst is selected, where strong bases will result in low Mw polymers and more specialized organometallic catalysts can be used for more control and higher Mw synthesis. The problem i notice with products like PEG (and products that have existed for a long time) kind of lose the availability of knowing their production process simply by looking online. The production is obviously already perfected industrially but the information is just not publicly available (understandable but annoying), it's just very common with products like this! Usually i will look for papers that came out from 1900-1960 and see how it was first done, they can work but will never achieve the same quality as the perfected processes that companies have developed behind closed doors. To know how exactly these things are done today you need to know someone personally who can tell you (if not under NDA) or work in the industry urself.
@@Chemiolis yes. The ethylene oxide polymerization is very nasty I've been told. That's why any other method to make it would be interesting at least for small scales. But I guess the 6-membered dioxane is very favored compared to PEG. Perhaps this may work with longer dialcohols. Great videos!
Did you use lithium for drying here for a reason or would sodium work?
Sodium works, i just didn't have any clean sodium around
Where are you getting these MASSIVE stir bars!?
All hail the king of low yields !!
What's the purpose of adding the metallic lithium in the final distillation?
It will react with water and dry the dioxane. I only did it because in the original vid he uses sodium, but i don’t think it’s really necessary. Drying it with sieves afterward is fine, and honestly putting a lot of effort to get super dry and pure dioxane is not really worth it unless u need it.
Very nice video, you seem to have access to a lot of hard to get chemicals though. How come you didn't just buy the dioxane?
When put in the separators funnel, is the dioxane the upper or lower layer?
Upper. Dioxane has higher density than water so generally you’d expect it to be the bottom layer, but saturating the water layer with KOH significantly increases its density so it will be on the bottom.
@@Chemiolis nice, thanks for the response
Can u discuss more details? Such as type of side products, how H2SO4 will make the BP of impurities low, why NaOH cause the impurities to polymerize? And thanks for ur efforts in these awesome videos
The main side product is acetaldehyde and its acetal with ethylene glycol
I love your aluminum Shrek
Simple dehydration seems like a really dirty and polymerization-prone way to attack this synthesis. Perhaps there's a higher yielding way to attack the alcohols one at a time?
Good synth, but might be worth it to toss a health and safety bit on this bad boy
Anyone know a good way to dry sodium hydroxide? I'm having trouble getting any that's not wet even straight out of a new container
bake it in the oven at like 200C or so for an hour, generally NaOH has like 10% water if you bought it as drian cleaner and works fine for drying dioxane
@@EdwardTriesToScience thanks mate, I'll give that a try.. i think the sodium hydroxide I'm getting might be even wetter than 10%, i tried to make sodium metal and it completely failed and ate half way through the bottom of the flask so I've definitely got a water problem
@@markshort9098 Just melt it in nickel, silver or pure iron can. In the last one you may obtain slightly brown substance but I think it's not a huge problem
@@dimaminiailo3723 that was my first thought but the problem I see with melting it is it'll need to be smashed up after which would take a while and it would be absorbing water out of the atmosphere the whole time.. I need it dry for making sodium metal so I think I'll get some lithium out of a battery to dry it chemically, a little lithium contamination shouldn't cause to many problems
@@markshort9098 The cake surface is pretty small so it doesn't look to absorb as many water as it was initially. Just try it and work as fast as possible!
Hold on I thought I was the king of low yield!!
Nile Red virsion 2
Very nicely done.. I just had an idea on why 1,4-Dioxane is considered to be carcinogenic. Isoelectronic with benzene was my thought. I don't understand Hückels rules well enough to confirm but I'm taking educated guess it substitutes for benzene.
It is not aromatic, no.
The next Nilered
I wish people would stop comparing the two. Nile seems to be in it for the money. Just reposts shorts of old videos. This is better.
@@bp8652 no he isn't he he takes time to make vids on his main channel just because chemiolis upload in a somewhat consistent manner doesn't mean that nilered doesn't do anything but I respect your opinion but to kill the time he upload shorts so we have something to watch but hey I get you
@@yasserotb1454 NileRed definitely puts a lot of effort in perfecting his content. The problem with a large project can also be that if you are halfway and it has completely gone wrong and u can't get it to work it will basically be useless and u wasted a lot of time. He also comes up with many methods himself these days which aren't easily laid out in papers, so it takes a lot of extra time. In a podcast i was listening he said he would stop focusing on main channel vids for now (he said he was tired of that style of content) and will focus on new style like shorts and NileBlue. (He said in patreon exclusive ep31 safety third podcast). Anyhow, i will just do whatever i feel like doing, but i don't have Nile's lab :'). Many things i just can't do (yet).
@@Chemiolis yup
@@Chemiolis Well that sucks. The shorts aren't nearly as good. If I wanted Tiktok I'd be on tiktok lol.
spicey
In your mechanism diagram, Diethylene glycol and the intermediates directly preceding and proceding it are all missing the 2nd carbon right of the central oxygen.
420 nice
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