Opylation
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Possible easy thionyl chloride synthesis
Hey all,
One of the chemicals I’ve been wanting to make for a while now is thionyl chloride. I’ve been doing some research and the original way I was going
to make it, using SCl2 + SO2 + Cl2 seems a little cumbersome. I have, however, seen a synthesis for thionyl chloride that uses phosgene. Now I know
phosgene is a gas and gases can be difficult to control, but this got me thinking. Diphosgene is a liquid and triphosgene is a solid. Maybe phosgene
can be replaced by one of these? Also diphosgene can be easily synth’ed using Cl2 + MeOOCH and daylight. Even better yet, SO2 and phosgene/
diphosgene are soluble in Chloroform. Could one possibly make a solution of SO2 (CHCl3) and add to diphosgene?
I am curious.
Let me know what you guys think!
Edit: it looks like diethyl ether might be a better solvent however I was unsure how SO2 or diphosgene would react with it
[Edited on 11-12-2019 by Opylation]
[Edited on 11-12-2019 by Opylation]
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woelen
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You want dead?
Phosgene is extremely dangerous. Only a very small amount is needed to screw up your lungs. Warning properties of the gas are mediocre at best. If you
smell it, then you're most likely screwed already.
I myself have worked quite a lot with true nasties in my home experiments (e.g. PCl5, PCl3, Cl2, even HCN), but I never had the "courage" to work with
COCl2. I have the chems to make this, but I never attempted to do this.
Diphosgene and triphosgene are a little less dangerous, because they are liquids, but their vapors also are very dangerous. Besides that, making
diphosgene from methylformiate and Cl2 is not easy at all. Do not expect the reaction to be fast and complete. You have to deal with incomplete
chlorination and side reactions.
Leave working with these to the pros, who have a well-equipped lab with adequate safety measures and who let people wear special phosgene-detection
batches.
Some years ago, someone from this forum died after COCl2-exposure (IIRC the member had username myfanwy). He used to make several dangerous reagents,
which went fine each time. This might have made him over-confident of his own capabilities. But, one day he went too far with making phosgene, and
passed away after suffering from severe pulmonary edema. He was still in his teens and we lost a very dedicated, but sometimes somewhat reckless,
member.
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Pumukli
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Use a bit more common sense!
If there was an easy, accessible route to thionyl-chloride then wouldn't it be already discovered? Why would the inorg. prep. books list those
cumbersome routes that are listed instead of a less demanding one - if such one existed?
How probable that your proposed route is a radically new one and never thought of by other, more knowledgeable chemists?
I don't want to dwell into things like safety, hazards, etc. Woelen already pointed it out.
May I ask what was the most complicated preparation you successfully carried out?
Very basic things can go wrong and a seemingly easy synth could become very challenging at times. Thionyl chloride synths are easy only on paper.
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draculic acid69
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Socl2 can be bought with some difficulty and made with sulfur compounds with some difficulty but it's not worth the risk of trying something as crazy
as phosgene synthesis to yeild it.
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Metacelsus
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Yeah, phosgene is no joke. There was an extra special safety training required by my university when I needed to use it a few years ago. (And that was
for a 20% solution in toluene. A gas cylinder of phosgene would be a whole different level of scary.)
Please don't kill yourself!
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Opylation
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Hey all,
I appreciate all of your concerns and I do just want to say that at this moment it is just theoretical. I just wanted to see what others thought of
the idea. I am very aware of the dangers of phosgene which is why I didn’t want to handle the gas at all. Also, this wouldn’t be attempted
anywhere else besides outside to avoid any accidental contact. I was thinking using diphosgene or triphosgene would be better as residence time in
liquids is by quite a large margin better than gases. But then again, that’s why I posted on here first before carrying anything out.
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Σldritch
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A crazy (but less so) idea is to make it from Trichlorosulfonium Hexachlorostannate ( (SCl3)2SnCl6 ) and Sulfur
Dioxide. I would imagine Sulfur Dioxide is too inert though.
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SWIM
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Doing it outside to be safe? Ypres was outside.
Phosgene was used as a war gas because it works well for killing people outside.
It's dense, it's insidious, it's also several other things I can't remember that make it more persistent than you'd think.
I would be much happier using phosgene than mustard gas, but that's a pretty low bar.
(Either can kill you, but the phosgene is less painful and leaves a prettier corpse.)
I'm not even crazy about using chlorine in any quantity, but with that stuff you KNOW when you're exposed.
Your more sophisticated war gasses are much sneakier.
I read somewhere that sub-lethal phosgene levels make cigarettes taste bad (described as metallic), but I'm not eager to find out for myself.
If you do screw around with this stuff bear in mind that activated charcoal filters will adsorb it, but they also release it back into the environment
slowly.
This means an activated charcoal only mask won't keep you alive through extended exposure.
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draculic acid69
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You will need a full spaceman suit type thing to be even near safe using phosgene.
Maybe a full body scuba wetsuit with an oxygen tank far far away from ppl and civilization.outside doesn't equal safe.
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Cou
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I think chemsavers sells to amateurs and residential addresses, not sure. Maybe they ship benign chemicals to amateurs, but are more picky about nasty
chemicals?
https://chemsavers.com/t/thionyl-chloride-99-100-ml/
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Dan Vizine
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Diphosgene and Triphosgene are simple to use, relatively safe direct replacements for phosgene in most reactions. We used it routinely in mediocre
fume hoods with simple carbon respirators to augment the protection. None of us ever had the slightest issue with it.
The awe in which phosgene is held is somewhat disrespectful to bromine. Bromine is easily in the same neighborhood of toxicity and few of us think
twice about using it. The use of di- and triphosgene makes potential exposures quite a tolerably low risk for any chemist of moderate or better
skills.
From CDC:
For bromine
It has been reported that 1.7 to 3.5 ppm produces severe choking, 4.5 to 9 ppm is extremely dangerous, and 30 ppm would prove fatal in a short time.
Current OSHA PEL: 0.1 ppm (0.7 mg/m3) TWA
For phosgene
Basis for original (SCP) IDLH: The chosen IDLH is based on the statement by Jacobs that 1 part in 200,000 (5 ppm) is probably lethal for exposures of
30 minutes. A level of 30 ppm is estimated to prove fatal in 17 minutes.
Current OSHA PEL: 0.1 ppm (0.4 mg/m3) TWA
In contrast to what woelen had suggested, merely detecting the odor of phosgene is of no big significance. I've smelled it numerous times. It smells
just like everybody who's smelled it in the past has said it does, like moldy hay.
[Edited on 12/18/2019 by Dan Vizine]
"All Your Children Are Poor Unfortunate Victims of Lies You Believe, a Plague Upon Your Ignorance that Keeps the Youth from the Truth They
Deserve"...F. Zappa
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Amos
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Thanks Dan, always nice to see someone experienced and with their wits about them ready to scare the bogeyman away. Give it a few more decades and
people will tell you of all the horrific threats nitrogen dioxide poses and how it must never, ever be synthesized. Anything outside the realm of the
more serious organometallics can probably be handled in a well-ventilated area by an experienced and level-headed amateur.
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DraconicAcid
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Quote: Originally posted by Dan Vizine  | | In contrast to what woelen had suggested, merely detecting the odor of phosgene is of no big significance. I've smelled it numerous times. It smells
just like everybody who's smelled it in the past has said it does, like moldy hay. |
I've often read in books that it smells like fresh-cut hay. The only time I've smelled it, it was like the rancid bottom of an old lawn mower, and it
took me surprisingly long to put connect the smell with the description.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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Dan Vizine
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Amos,
So true. I've made liquid hydrogen cyanide (170 g) and bromine (1 kg/run) in my basement with no fume hood. I have no ill effects to show for it.
Joints are all ground glass, all joints are well greased, the joints are secured with Keck clamps, all glassware is suitable supported and a vent tube
runs from the apparatus to the great outdoors. I wear a respirator, work behind a Plexiglas shield as needed and I've been doing it for a long, long
time. I think my first job taught me a lot, if you didn't look out for your own safety there, nobody did it for you.
Draconic acid, it's unique, isn't it? The smell always reminds me of fall the same way that the smell of HCN reminds me of Thanksgiving.
[Edited on 12/18/2019 by Dan Vizine]
"All Your Children Are Poor Unfortunate Victims of Lies You Believe, a Plague Upon Your Ignorance that Keeps the Youth from the Truth They
Deserve"...F. Zappa
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SWIM
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| Quote: Originally posted by Dan Vizine |
The smell always reminds me of fall the same way that the smell of HCN reminds me of Thanksgiving.
[Edited on 12/18/2019 by Dan Vizine] |
Wow, that is a great quote.
Fair warning: If I ever write anything with an organic chemist character, I'm probably gonna steal it.
[Edited on 19-12-2019 by SWIM]
Oh, BTW: the Chemsavers link says commercial addresses only.
I don't know if the commercial address also has to be somewhere that might actually have a reason to buy stuff like that.
Like getting it delivered to the fish and chips shop you own, or your friend's office (He's a chartered accountant, don't you know), might not work.
[Edited on 19-12-2019 by SWIM]
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Dan Vizine
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This is pretty much just an academic discussion anyway. The cost of these phosgene precursors is quite high and their availability is such that
anybody able to buy one of them could just as easily buy the thionyl chloride.
"All Your Children Are Poor Unfortunate Victims of Lies You Believe, a Plague Upon Your Ignorance that Keeps the Youth from the Truth They
Deserve"...F. Zappa
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DraconicAcid
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| Quote: Originally posted by Dan Vizine | | Draconic acid, it's unique, isn't it? The smell always reminds me of fall the same way that the smell of HCN reminds me of Thanksgiving.
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Unique among chemicals, sure. It doesn't remind me of fall, though- I never did much mowing of lawns after high school, and that was always over the
summer (I grew up in the north, beyond The Wall, where grass simply stopped growing two weeks into September).
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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Mush
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| Quote: Originally posted by Opylation | Hey all,
One of the chemicals I’ve been wanting to make for a while now is thionyl chloride. I’ve been doing some research and the original way I was going
to make it, using SCl2 + SO2 + Cl2 seems a little cumbersome. I have, however, seen a synthesis for thionyl chloride that uses phosgene. Now I know
phosgene is a gas and gases can be difficult to control, but this got me thinking. Diphosgene is a liquid and triphosgene is a solid. Maybe phosgene
can be replaced by one of these? Also diphosgene can be easily synth’ed using Cl2 + MeOOCH and daylight. Even better yet, SO2 and phosgene/
diphosgene are soluble in Chloroform. Could one possibly make a solution of SO2 (CHCl3) and add to diphosgene?
I am curious.
Let me know what you guys think!
Edit: it looks like diethyl ether might be a better solvent however I was unsure how SO2 or diphosgene would react with it
[Edited on 11-12-2019 by Opylation]
[Edited on 11-12-2019 by Opylation] |
Playing with war gases at home ? Forget about it.
If they managed to f***k up and kill their employee, you will def. kill yourself and others.
Fatal Exposure: Tragedy at DuPont
https://www.youtube.com/watch?v=ISNGimMXL7M
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XeonTheMGPony
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| Quote: Originally posted by Mush |
If they managed to f***k up and kill their employee, you will def. kill yourself and others.
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and yet people kill them self's every day with water, I am afraid to tell you, life ultimately will kill you too!
If you think you can do it, go for it, your body your right to do what ever you please with it, just do your due research and warn those around who
may come to investigate should you keel over
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Mush
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| Quote: Originally posted by XeonTheMGPony | | Quote: Originally posted by Mush |
If they managed to f***k up and kill their employee, you will def. kill yourself and others.
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and yet people kill them self's every day with water, I am afraid to tell you, life ultimately will kill you too!
If you think you can do it, go for it, your body your right to do what ever you please with it, just do your due research and warn those around who
may come to investigate should you keel over |
What is this mumbo-jumbo? I don't get it.
Did you watch the video, btw? I don't think so.
Please elaborate . I would like to know more about deaths caused by water vapour in 50 ppm concentration.
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Texium
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Thread Moved
13-1-2020 at 17:20 |
XeonTheMGPony
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| Quote: Originally posted by Mush | | Quote: Originally posted by XeonTheMGPony | | Quote: Originally posted by Mush |
If they managed to f***k up and kill their employee, you will def. kill yourself and others.
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and yet people kill them self's every day with water, I am afraid to tell you, life ultimately will kill you too!
If you think you can do it, go for it, your body your right to do what ever you please with it, just do your due research and warn those around who
may come to investigate should you keel over |
What is this mumbo-jumbo? I don't get it.
Did you watch the video, btw? I don't think so.
Please elaborate . I would like to know more about deaths caused by water vapour in 50 ppm concentration. |
Well as I thought, you don't think well!
I seen that video year ago and a great many more, I have seen worse at real time, and I seen people die from a simple every day trivial mistake.
For some reason I feel no need to cower in a closet and cry.
If the user uses their mind, researches and does things carefully they are no more in danger then any other substance in every day life.
They just need t be aware the dangers are very real and take proper percuations.
[Edited on 14-1-2020 by XeonTheMGPony]
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chemplayer...
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Unless you've got a pro-lab set-up, probably an approach to steer clear of:
http://www.sciencemadness.org/talk/viewthread.php?tid=54656
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morganbw
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Yea, for most of us. I doubt that I will be dealing with it but there is literature that does go over some things. One thing for sure, is do not piss
in the wind.
Do nothing unless it is researched and your confidence is high.
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XeonTheMGPony
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| Quote: Originally posted by morganbw |
Yea, for most of us. I doubt that I will be dealing with it but there is literature that does go over some things. One thing for sure, is do not piss
in the wind.
Do nothing unless it is researched and your confidence is high. |
^^^^^^^^^^^^^ That is the proper answer to any dangerous procedure.
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