Sciencemadness Discussion Board

Theoretical Synthesis of Phosgene

Agari - 8-10-2015 at 19:16

I am going to try out an experiment on possibly synthesizing phosgene,and am actually going to wear a respirator unlike another member that died in 2010.
Note: So far,this is just a theory,what does the community think of this?
Chemicals:
-Crushed up TCCA tablets or calcium hypochlorite
-35% hydrochloric acid
-Activated carbon bought at a pharmacy
-95% Sulfuric acid
-85% Formic acid
-Water to neutralize the gas
Procedure:
-I will add the TCCA or CaCl2O2 to a 3-neck flask
-Will fill up a reaction tube with activated carbon halfway
-Add formic acid to another 3-neck flask
-I will then seal one end of the reaction tube with a 2-hole stopper and the other end with a 1-hole stopper.
-I will then attach an addition funnel to the 3-neck with formic acid and fill it with sulfuric acid, then completely seal 1 of the necks and cover the other with a 1-hole stopper.The ratio of formic to sulfuric acid is 1:1.
-Attach another addition funnel with Hydrochloric acid to the 3-neck flask and seal one end completely and the other end with a 1-hole stopper.
-Connect the 1-hole end of the reaction tube to a tub of water using rubber tubing to hydralize any phosgene,if any, that exits.
-I will finally open the stopcocks of both addition funnels.
-I will then connect the 2 3-neck flasks to the reaction tube using rubber tubing and start heating the reaction tube with either a blowtorch or a Bunsen burner.
Since the reaction is exothermic,I will use water to cool off the reaction tube and (hopefully) keep the temperature below 200C while above 110C.
The process(Theoretically):
The sulfuric acid will dehydrate the formic and result in carbon monoxide gas and the byproducts will remain in the flask.
If TCCA is used with the HCl,then the following happens:
3 HCl + C3Cl3N3O3 = 3 CNOH + 6 Cl
If CaCl2O2 is used:
CaCl2O2 + 4 HCl = CaCl2 + 2 H2O + 2 Cl2
Then,with the CO and Cl flowing into the reaction tube,the reaction:
CO+ Cl2-->COCl2
Will occur, and is catalyzed by the activated carbon.
The phosgene product then flows out of the reaction tube and into the water tub and is then decomposed to Carbon dioxide and hydrogen chloride:
COCl2 + H2O → CO2 + 2 HCl
Thus neutralizing the gas,well technically hydralizing.

As a precaution,I will use a respirator since phosgene is a level 4 health hazard on the NFPA 704 standard,meaning that small doses are enough to kill or cause major residual damage.
This is just a theory,any criticism is welcome.

By the way,I heard what happened to myfanwy,I also heard that he was synthesizing hydrogen cyanide.

[Edited on 9-10-2015 by Agari]

[Edited on 9-10-2015 by Agari]

phlogiston - 9-10-2015 at 03:33

The title does not match your post. The title suggests you are only interested in theory (a thought experiment) but your post suggests that you intend to execute the experiment.

Why would you want to?
If your only goal is to do this to be able to claim you did you will need a method of detecting the product, to prove that you actually were sucesfull.
IMHO certain chemicals are not suitable for experimentation by amateurs. War gasses certainly fall into that category (not counting chlorine, which can be handled in small quantities with sufficient care)

I can only hope you are not planning to do this in any residential area or location where other people (or animals) could be present.
Consider if your method of neutralizing the product is sufficiently effective and fail-safe.

[Edited on 9-10-2015 by phlogiston]

Dr.Bob - 9-10-2015 at 06:43

On the theoretical side, what is the reaction rate of the reaction

CO+ Cl2-->COCl2

If it is not nearly instant, then trying to make it in a flow system, without ways to measure and control the flow, concentration, and reaction time of the gases, it will be hard to make much useful phosgene. Most people using small amounts of it now use either diphosgene or triphosgene (see wikipedia or Aldrich's website) as replacements, which are easier to measure, store, handle, and safely use than phosgene. I have used all three and would use triphosgene any day over a cylinder of phosgene (we had ~100 pounds of it in the lab in grad school) or even a solution of it in a solvent (which you can buy from some vendors) or any other method of making it. And there are somewhat more practical ways of making them which are safer than the method above. Still not easy, but still better.

Also, many reactions that needs phosgene can be redesigned for other more practical reagents or methods. But for some reactions, nothing is better, I will admit.

Agari - 9-10-2015 at 13:04

Quote: Originally posted by phlogiston  
The title does not match your post. The title suggests you are only interested in theory (a thought experiment) but your post suggests that you intend to execute the experiment.

Why would you want to?
If your only goal is to do this to be able to claim you did you will need a method of detecting the product, to prove that you actually were sucesfull.
IMHO certain chemicals are not suitable for experimentation by amateurs. War gasses certainly fall into that category (not counting chlorine, which can be handled in small quantities with sufficient care)

I can only hope you are not planning to do this in any residential area or location where other people (or animals) could be present.
Consider if your method of neutralizing the product is sufficiently effective and fail-safe.

[Edited on 9-10-2015 by phlogiston]

I will use small amounts of the acids and TCCA/HCl,and possibly use a detector to confirm that synthesis was successful somewhere along the line before hydrolysis occurs. I am not sure whether hydrolysis is a very effective neutralization method,but it should reduce the amount of gas to a level that does not present a threat to the surroundings,or do it inside but ventilate the area well.
https://www.youtube.com/v/K5NuqpdYDhE








[Edited on 9-10-2015 by Agari]

clearly_not_atara - 9-10-2015 at 13:29

Diphosgene via methyl formate + Cl2/hv sounds like a massive win relative to other methods, if you have the appropriate equipment, that is. Obviously do not attempt the procedure without reading the original reference; in particular, do not attempt to simply substitute methyl formate for methyl chloroformate in the OrgSyn procedure unless you have consulted other references which use specifically methyl formate.

Methyl formate is relatively easy to produce, but I would avoid the Fischer esterification; prefer the MeBr + NaHCO2 to avoid generating CO gas.
Quote:
If it is not nearly instant, then trying to make it in a flow system, without ways to measure and control the flow, concentration, and reaction time of the gases, it will be hard to make much useful phosgene.


In addition, be aware that CO is generally an underrated toxicant. Your system as described has very little in the way of containment or detection for CO and I am concerned that you have not adequately considered the risks of working with this odorless, colorless, extremely toxic, insoluble-in-almost-everything gas.

In fact if you run the reaction as you have described it your CO will pass through the charcoal and the water and exit into your laboratory atmosphere. Study the containment and safety procedures for carbon monoxide before proceeding.

[Edited on 9-10-2015 by clearly_not_atara]

aga - 9-10-2015 at 14:40

There is no actual stated Use for the lethal gas.

Perhaps you wish to scale up and kill a lot of people ?

That's the first thought that springs to mind.

Phosgene is not suited to Amateur Chemistry at all.

clearly_not_atara - 9-10-2015 at 15:08

Quote:
[quote=aga] There is no actual stated Use for the lethal gas. [...] Phosgene is not suited to Amateur Chemistry at all.


I object. Phosgene, if properly handled, can render the synthesis of many otherwise inaccessible compounds -- including 2-oxazolidinones, cyclic and acyclic alkyl carbonates, acyl/imidoyl/oxalyl chlorides, chloroformates, BOC/tBOC/fMOC-protected amines/alcohols, peralkylated amidines/guanidines/ureas, and oddities like isatoic anhydride -- possible from stable and cheap precursors. Alternatives like SOCl2 are similarly difficult to prepare and carry their own hazards.

At worst phosgene can be quantitatively converted to carbonyl-diimidazole, a relatively safe and mostly stable coupling reagent (can prepare esters, amides, thioesters, anhydrides).

Of course you are more likely to end up synthesizing carbonyl-dichemist if you aren't careful. I wouldn't fuck with it, myself.

[Edited on 9-10-2015 by clearly_not_atara]

Agari - 9-10-2015 at 16:37

Quote:
Quote: Originally posted by clearly_not_atara  
[quote=aga] There is no actual stated Use for the lethal gas. [...] Phosgene is not suited to Amateur Chemistry at all.


I object. Phosgene, if properly handled, can render the synthesis of many otherwise inaccessible compounds -- including 2-oxazolidinones, cyclic and acyclic alkyl carbonates, acyl/imidoyl/oxalyl chlorides, chloroformates, BOC/tBOC/fMOC-protected amines/alcohols, peralkylated amidines/guanidines/ureas, and oddities like isatoic anhydride -- possible from stable and cheap precursors. Alternatives like SOCl2 are similarly difficult to prepare and carry their own hazards.

At worst phosgene can be quantitatively converted to carbonyl-diimidazole, a relatively safe and mostly stable coupling reagent (can prepare esters, amides, thioesters, anhydrides).

Of course you are more likely to end up synthesizing carbonyl-dichemist if you aren't careful. I wouldn't fuck with it, myself.

[Edited on 9-10-2015 by clearly_not_atara]


Hmm,that sounds rather interesting, any way to increase phosgene yield for something like that? While I am unlikely to actually be able to prepare those compounds,my initial intended use for the gas was to pipe it over into a concentrated ammonia solution to obtain urea,but I later found out that I would need anhydrous ammonia otherwise most of the gas will be hydrolyzed.
Edit:If I can't increase the yield in any way,I guess I will have to buy a generator from Sigma Aldrich's site.

[Edited on 10-10-2015 by Agari]

careysub - 9-10-2015 at 16:50

Check out my recent post on the hazard of phosgene, compared to hydrogen cyanide:
http://www.sciencemadness.org/talk/viewthread.php?tid=13590

Phosgene is much more dangerous than hydrogen cyanide due to the fact that phosgene is a cumulative poison, and cyanide isn't.

Phosgene is a very useful reagent, widely used in industry.

But it should only be produced and consumed in a carefully set-up closed system, with provision against any release (an alkali/water solution trap), and with suitable respirator protection (separate air supply, an efficient fume hood, or a mask with a filter known to be effective against phosgene) since accidents happen.

Phosgene has little odor, provides no warning signs, produces no symptoms for up to 48 hours, and once they appear you are already a dead man. There is no treatment.

A phosgene detection badge would be nice also (commercially available).

You can prepare your own with accessible reagents (this is from Sartori's "The War Gases"):
"Method using Dimethyl Amino Benzaldehyde—Diphenylamine
Paper. Phosgene, even if present in traces in the air, can be
detected by means of papers prepared with dimethyl amino
benzaldehyde and diphenylamine.
These papers are prepared by immersing strips of filter paper
in a solution of 5 gm. />-dimethyl-amino-benzaldehyde and 5 gm.
diphenylamine in 100 ml. ethyl alcohol and allowing them to dry
in a dark place, or better still, according to Suchier, in an
atmosphere of carbon dioxide. By exposing these papers, which
are originally white or pale straw-yellow, to an atmosphere
containing phosgene, an orange-yellow colouration is produced in
a few seconds, the intensity of the colour varying with the
concentration of phosgene. This change of colour is also observed
in presence of chlorine or hydrochloric acid.
It is possible to detect phosgene at a concentration of 4 mgm.
per cu. m. of air"

Agari - 9-10-2015 at 17:19

Quote: Originally posted by careysub  
Check out my recent post on the hazard of phosgene, compared to hydrogen cyanide:
http://www.sciencemadness.org/talk/viewthread.php?tid=13590

Phosgene is much more dangerous than hydrogen cyanide due to the fact that phosgene is a cumulative poison, and cyanide isn't.

Phosgene is a very useful reagent, widely used in industry.

But it should only be produced and consumed in a carefully set-up closed system, with provision against any release (an alkali/water solution trap), and with suitable respirator protection (separate air supply, an efficient fume hood, or a mask with a filter known to be effective against phosgene) since accidents happen.

Phosgene has little odor, provides no warning signs, produces no symptoms for up to 48 hours, and once they appear you are already a dead man. There is no treatment.

A phosgene detection badge would be nice also (commercially available).

You can prepare your own with accessible reagents (this is from Sartori's "The War Gases"):
"Method using Dimethyl Amino Benzaldehyde—Diphenylamine
Paper. Phosgene, even if present in traces in the air, can be
detected by means of papers prepared with dimethyl amino
benzaldehyde and diphenylamine.
These papers are prepared by immersing strips of filter paper
in a solution of 5 gm. />-dimethyl-amino-benzaldehyde and 5 gm.
diphenylamine in 100 ml. ethyl alcohol and allowing them to dry
in a dark place, or better still, according to Suchier, in an
atmosphere of carbon dioxide. By exposing these papers, which
are originally white or pale straw-yellow, to an atmosphere
containing phosgene, an orange-yellow colouration is produced in
a few seconds, the intensity of the colour varying with the
concentration of phosgene. This change of colour is also observed
in presence of chlorine or hydrochloric acid.
It is possible to detect phosgene at a concentration of 4 mgm.
per cu. m. of air"

If you read my original post,I stated that I was going to use a respirator,though I am not sure if mine is effective vs phosgene. As for detection addressed in an above reply,I was going to use a safe-air badge, which I will order tomorrow online. It is quite late where I live,I will try to make phosgene detection paper tomorrow if I can get my hands on the reagents.

[Edited on 10-10-2015 by Agari]

BromicAcid - 9-10-2015 at 17:23

Quote: Originally posted by Agari  

-Water to neutralize the gas

-Connect the 1-hole end of the reaction tube to a tub of water using rubber tubing to hydralize any phosgene,if any, that exits.


I... there is a very real chance you could die with this level of misunderstanding. You're using water to scrub your exit gasses... Carbon monoxide will not scrub with water and your mask likely won't help either. Chlorine will not scrub with water, the solubility is actually surprisingly low in plain old water, plus it may make it past your filter. And phosgene <b> will not scrub with water</b>. Phosgene is actually not very reactive with water at all and can be dissolved in water without reaction (and is only very slightly soluble). Please stop using the internet and go out and buy a book, get a reliable primary reference and stick to that. The belief that phosgene is rapidly hydrolyzed is ridiculously wide-spread and completely false.

Agari - 9-10-2015 at 17:33

Quote: Originally posted by BromicAcid  
Quote: Originally posted by Agari  

-Water to neutralize the gas

-Connect the 1-hole end of the reaction tube to a tub of water using rubber tubing to hydralize any phosgene,if any, that exits.


I... there is a very real chance you could die with this level of misunderstanding. You're using water to scrub your exit gasses... Carbon monoxide will not scrub with water and your mask likely won't help either. Chlorine will not scrub with water, the solubility is actually surprisingly low in plain old water, plus it may make it past your filter. And phosgene <b> will not scrub with water</b>. Phosgene is actually not very reactive with water at all and can be dissolved in water without reaction (and is only very slightly soluble). Please stop using the internet and go out and buy a book, get a reliable primary reference and stick to that. The belief that phosgene is rapidly hydrolyzed is ridiculously wide-spread and completely false.

Mmmk,I was not actually planning on scrubbing chlorine and carbon monoxide,just the phosgene,oh well,so long for that.

careysub - 9-10-2015 at 17:57

A two stage scrubbing system using NaOH/sodium thiosulfate and (separately) KOH/KMnO4 should scrub phosgene, chlorine and carbon monoxide.

Agari - 9-10-2015 at 18:45

Quote: Originally posted by careysub  
A two stage scrubbing system using NaOH/sodium thiosulfate and (separately) KOH/KMnO4 should scrub phosgene, chlorine and carbon monoxide.

I will consider that,I know that NaOH will scrub chlorine and KMnO4 will oxidize the CO,and phosgene does decompose with NaOH.


[Edited on 10-10-2015 by Agari]

clearly_not_atara - 9-10-2015 at 21:50

Quote:
Hmm,that sounds rather interesting, any way to increase phosgene yield for something like that? While I am unlikely to actually be able to prepare those compounds,my initial intended use for the gas was to pipe it over into a concentrated ammonia solution to obtain urea,but I later found out that I would need anhydrous ammonia otherwise most of the gas will be hydrolyzed.
Edit:If I can't increase the yield in any way,I guess I will have to buy a generator from Sigma Aldrich's site.


Orgsyn has a procedure:

http://www.orgsyn.org/demo.aspx?prep=cv5p0201

I suggest an excess of imidazole; better safe than acylated. I (and everyone else here) cannot stress enough the extreme danger you're putting yourself into.

phlogiston - 10-10-2015 at 02:47

Doesn't know if his scrubber is effective at all ... check
Quote: Originally posted by Agari  

I am not sure whether hydrolysis is a very effective neutralization method


Does not know if his respirator is any good for the purpose ... check
Quote:

I was going to use a respirator,though I am not sure if mine is effective vs phosgene


Completely ignores the other highly poisonous gasses being produced... check
Quote:

I was not actually planning on scrubbing chlorine and carbon monoxide


And is already planning to scale up before he even started...
Quote:
Hmm,that sounds rather interesting, any way to increase phosgene yield



At least you did one thing right, which was posting here before actually doing this. It may safe your life, because you are certainly on a dangerous path.
First, consider whether you really want to pursue this. Is making urea truly worth it (considering it is cheap and should be easily available almost anywhere)??
Then, if you decide you do, spend the next year doing nothing but planning and thinking it over before doing anything. Pay extreme consideration to detail and possible failure mechanisms. How do you check if your respirator seals well? Can the tubing on your scrubber come lose in case of overpressure? What is the capacity of the scrubber? What if you trip, hit your head and lose consciousness? Where does your fumehood vent extracted fumes? How are you controlling the gasflow of the reactants? etc. etc. etc.

Metacelsus - 10-10-2015 at 06:11

Quote: Originally posted by Agari  
my initial intended use for the gas was to pipe it over into a concentrated ammonia solution to obtain urea


If you're making phosgene, at least use it for something better than making urea. Make something that can only be made with phosgene, like ethyl chloroformate, from reaction with ethanol. (Don't say you can't prepare that.)

BromicAcid - 10-10-2015 at 06:31

If you are hell-bent on making phosgene you should explore different routes. Working with a single gas is doable at home but taming two gasses to make a third is begging for disaster. Older (much older) methods started from chloroform or carbon tetrachloride. It may suit you better to start there, at least you could better meter your reagents that way plus you wont have unreacted chlorine and carbon monoxide coming out the back end.

careysub - 10-10-2015 at 07:56

While doing a little research on this subject, I see that oxalyl chloride can decompose into phosgene and carbon monoxide in various side reactions.

I did not know that.

It would seem anyone working with oxalyl chloride should at least have the respirator/fume hood in place and a phosgene badge also.

jnik - 10-10-2015 at 09:07

There is another possible way (probably more safe) to use triphosgene, which is a white-crystall solid with melting point near 80 C. After hydrolysis it will give you the desired compoud - phosgene. Such a solid substance much easier to handle.

To produce it you need to chlorinate dimethylcarbonate in a flask under irradiation of sunlight spectrum lamp with increase of temperature step by step from 40 to 80 C. Byproducts (HCl and unreacted chlorine) coud be neutralised with NaOH + Na2SO3 solution. End of reaction - green colour of gas phase above the liquid surface / yellow colour of the reaction mixture. Possible issues - crystallization of triphosgene in connection tubes and condenser.

Safety:
Actually phosgene is not THAT bad, so it will not kill you immediatly (good news). You have some time to neutralise yourself and lab. But be careful, phosgene will decrease your ability to sence it after exposure!!! (bad news) If you smell the substance, then you must stop process and find a leakage.

Implementing such a proccess you shoud prepare your best friend: respirator, gloves, neutralisation solutions (5-10% NH3 in water and/or organic amines like diethylamine) and alcohol (to inhale and drink).

Agari - 10-10-2015 at 10:08

Quote: Originally posted by jnik  
There is another possible way (probably more safe) to use triphosgene, which is a white-crystall solid with melting point near 80 C. After hydrolysis it will give you the desired compoud - phosgene. Such a solid substance much easier to handle.

To produce it you need to chlorinate dimethylcarbonate in a flask under irradiation of sunlight spectrum lamp with increase of temperature step by step from 40 to 80 C. Byproducts (HCl and unreacted chlorine) coud be neutralised with NaOH + Na2SO3 solution. End of reaction - green colour of gas phase above the liquid surface / yellow colour of the reaction mixture. Possible issues - crystallization of triphosgene in connection tubes and condenser.

Safety:
Actually phosgene is not THAT bad, so it will not kill you immediatly (good news). You have some time to neutralise yourself and lab. But be careful, phosgene will decrease your ability to sence it after exposure!!! (bad news) If you smell the substance, then you must stop process and find a leakage.

Implementing such a proccess you shoud prepare your best friend: respirator, gloves, neutralisation solutions (5-10% NH3 in water and/or organic amines like diethylamine) and alcohol (to inhale and drink).

I have serious doubts about inhaling ethanol when phosgene may be present in my lungs,correct me if I am wrong,but I'm pretty sure it will form HCl and other compounds.
Edit:Or MAYBE triphosgene is commercially available,nevermind,dimethyl carbonate is also commercially available.

[Edited on 10-10-2015 by Agari]

CharlieA - 10-10-2015 at 18:43

50-some odd years ago, I used phosgene in a synthesis of (I don't remember) at a then-subsidiary of Sigma Chemical Co. IIRC, we purchased the phosgene in small cylinders. In hindsight, I'm amazed that I didn't die in the laboratory, and now I'm a proud 12+ year cancer survivor. My oncologist thinks my smoking was the cause; my radiologist thinks my lab work was a cause. When I think of how I (we) operated in the lab (e.g., I pipetted just about anything by mouth; after a large (several kg) filtration involving EtOH and Et2O in a small enclosure I was bombed out of my head). I guess what I am trying to say is that it seems to me that many of our members do not give enough consideration to the hazards of chemistry. Although I am setting up a home lab after 35+ years of no chemical activity, I hope I am going slowly and giving careful consideration to my actions. Of course, maybe I am going too slowly...:(

Agari - 10-10-2015 at 18:57

Quote: Originally posted by CharlieA  
50-some odd years ago, I used phosgene in a synthesis of (I don't remember) at a then-subsidiary of Sigma Chemical Co. IIRC, we purchased the phosgene in small cylinders. In hindsight, I'm amazed that I didn't die in the laboratory, and now I'm a proud 12+ year cancer survivor. My oncologist thinks my smoking was the cause; my radiologist thinks my lab work was a cause. When I think of how I (we) operated in the lab (e.g., I pipetted just about anything by mouth; after a large (several kg) filtration involving EtOH and Et2O in a small enclosure I was bombed out of my head). I guess what I am trying to say is that it seems to me that many of our members do not give enough consideration to the hazards of chemistry. Although I am setting up a home lab after 35+ years of no chemical activity, I hope I am going slowly and giving careful consideration to my actions. Of course, maybe I am going too slowly...:(


Yep,TOTALLY legit,TOTALLY not full of crap.

Bot0nist - 10-10-2015 at 19:06

CharlieA, in this thread, I think your plea for a safe pace is called for, and that comes from an amateur whose intrest began with energetic materials.

I do hope the OP reconsider his quest, or at least takes a very slow pace in learning and applying the vast amount of knowledge and care that an amatuer hobbiest must surely have in order to even try to safely produce and work with an insidious killer like phosgene. Most amateurs and home chemistry enthusiasts would not even consider attempting such things, myself included.

In my more careless experiances, I have had organic peroxides explode unexpectedly in close proximity, gassed myself with nitrogen oxides, and even flirted with hazards such as hydrazine and azides, but still I would not have dared play with a devil like phosgene. And maybe some will say I am exaggerating the risks of this gas.

Perhaps it is "Not THAT bad," sure, when compared to modern nerve agents and war gasses, but it can and will easily be the unsuspecting death of you, and any poor soul unlucky enough to catch a few breaths of it. And that's if the attempt is successful. Carbon monoxide is a sneaky killer as well, and even a system failure resulting in a room full of chlorine could spell disaster.

[Edited on 11-10-2015 by Bot0nist]

Bot0nist - 10-10-2015 at 19:14

Quote: Originally posted by Agari  

Yep,TOTALLY legit,TOTALLY not full of crap.


I do hope your safety checks and PPE serve you as well as your sarcasm and disregard for what seemed to me to be honest and legitimate concern.
Good luck, and be safe Agari, and I mean that truely and with no ill will.

[Edited on 11-10-2015 by Bot0nist]

Agari - 10-10-2015 at 19:17

Quote: Originally posted by Bot0nist  
CharlieA, in this thread, I think your plea for a safe pace is called for, and that comes from an amateur whose intrest began with energetic materials.

I do hope the OP reconsider his quest, or at least takes a very slow pace in learning and applying the vast amount of knowledge and care that an amatuer hobbiest must surely have in order to even try to safely produce and work with an insidious killer like phosgene. Most amateurs and home chemistry enthusiasts would not even consider attempting such things, myself included.

In my more careless experiances, I have had organic peroxides explode unexpectedly in close proximity, gassed myself with nitrogen oxides, and even flirted with hazards such as hydrazine and azides, but still I would not have dared play with a devil like phosgene. And maybe some will say I am exaggerating the risks of this gas.

Perhaps it is "Not THAT bad," sure, when compared to modern nerve agents and war gasses, but it can and will easily be the unsuspecting death of you, and any poor soul unlucky enough to catch a few breaths of it. And that's if the attempt is successful. Carbon monoxide is a sneaky killer as well, and even a system failure resulting in a room full of chlorine could spell disaster.

[Edited on 11-10-2015 by Bot0nist]

Perhaps I will try using triphosgene to obtain the gas,rather than chlorine and carbon monoxide, or at least use low amounts of formic&sulfuric acid if I do in fact go for my old method.

Agari - 10-10-2015 at 19:28

Quote: Originally posted by Bot0nist  
Quote: Originally posted by Agari  

Yep,TOTALLY legit,TOTALLY not full of crap.


I do hope your safety checks and PPE serve you as well as your sarcasm and disregard for what seemed to me to be honest and legitimate concern.
Good luck, and be safe Agari, and I mean that truely and with no ill will.

[Edited on 11-10-2015 by Bot0nist]

I was talking about the part where he states that he worked for what used to be Aldrich Co.

Pyrovus - 11-10-2015 at 04:48

Quote: Originally posted by Agari  
Quote: Originally posted by jnik  
There is another possible way (probably more safe) to use triphosgene, which is a white-crystall solid with melting point near 80 C. After hydrolysis it will give you the desired compoud - phosgene. Such a solid substance much easier to handle.

To produce it you need to chlorinate dimethylcarbonate in a flask under irradiation of sunlight spectrum lamp with increase of temperature step by step from 40 to 80 C. Byproducts (HCl and unreacted chlorine) coud be neutralised with NaOH + Na2SO3 solution. End of reaction - green colour of gas phase above the liquid surface / yellow colour of the reaction mixture. Possible issues - crystallization of triphosgene in connection tubes and condenser.

Safety:
Actually phosgene is not THAT bad, so it will not kill you immediatly (good news). You have some time to neutralise yourself and lab. But be careful, phosgene will decrease your ability to sence it after exposure!!! (bad news) If you smell the substance, then you must stop process and find a leakage.

Implementing such a proccess you shoud prepare your best friend: respirator, gloves, neutralisation solutions (5-10% NH3 in water and/or organic amines like diethylamine) and alcohol (to inhale and drink).

I have serious doubts about inhaling ethanol when phosgene may be present in my lungs,correct me if I am wrong,but I'm pretty sure it will form HCl and other compounds.
Edit:Or MAYBE triphosgene is commercially available,nevermind,dimethyl carbonate is also commercially available.

[Edited on 10-10-2015 by Agari]


In the scheme of things HCl is not that bad. Sure, it's not a good idea to make a habit of breathing it in, but compared to phosgene it's pretty benign. HCl will hydrolyse proteins, but acid hydrolysis of proteins tends to be pretty slow. Phosgene on the other hand will quite effectively cross-link proteins by reacting with the nucleophilic NH2 groups, which will among other things drastically alter their structure, rendering them non-functional, and when enough critical proteins are affected, cell death results. Breathing in nucleophiles to react with the phosgene before it can react with the proteins in your lungs would prevent far more damage than any produced HCl would cause, the issue of course is how much phosgene can be eliminated this way, especially since breathing in ethanol and/or ammonia/alkylamines is not that healthy and thereby limits the amounts that can be used. Best not to get into that situation in the first place, in my opinion.

Darkstar - 11-10-2015 at 05:05

I've had lungs full of HCl before. And as unpleasant of an experience as it was, I'd take HCl over phosgene any day.

BromicAcid - 11-10-2015 at 07:58

This thread is getting ridiculous with too much speculation and minimization of the hazards of this and other compounds. Certainly MSDS can over exaggerate chemical hazards, but do not forget that this was and still can be used as a war gas. People working this this, experienced people, have died. Diphosgene and triphosgene are phosgene equivalents, they handle better because they are liquids and solids respectively but when using them one of the first steps is to either react them with a nucleophile or heat them to free up the phosgene. This can happen suddenly in some circumstances, not that they are much healthier on their own, diphosgene itself can be used as a chemical weapon just like its parent compound. Triphosgene, though a solid still generates enough phosgene just existing that it can trip local phosgene alarms when the container is opened. Please give these compounds the respect they deserve.

@Agari - Why would you doubt that that individual worked at Aldrich? You think there aren't other people on this forum that work or have worked at Aldrich or another large chemical company? I am not sure of the number of 'professionals' on this board but based on some of the polls it is apparently more than you think.

aga - 11-10-2015 at 09:01

We're not all teenagers here either.

I was last a teenager 29 years ago.

Enough time to have worked for Sigma Aldrich, ICI, BASF, Dow and Dupont for about 6 years each (albeit as a cleaner, given my lack of chemistry expertise !).

Agari - 11-10-2015 at 18:21

Quote: Originally posted by BromicAcid  
This thread is getting ridiculous with too much speculation and minimization of the hazards of this and other compounds. Certainly MSDS can over exaggerate chemical hazards, but do not forget that this was and still can be used as a war gas. People working this this, experienced people, have died. Diphosgene and triphosgene are phosgene equivalents, they handle better because they are liquids and solids respectively but when using them one of the first steps is to either react them with a nucleophile or heat them to free up the phosgene. This can happen suddenly in some circumstances, not that they are much healthier on their own, diphosgene itself can be used as a chemical weapon just like its parent compound. Triphosgene, though a solid still generates enough phosgene just existing that it can trip local phosgene alarms when the container is opened. Please give these compounds the respect they deserve.

@Agari - Why would you doubt that that individual worked at Aldrich? You think there aren't other people on this forum that work or have worked at Aldrich or another large chemical company? I am not sure of the number of 'professionals' on this board but based on some of the polls it is apparently more than you think.

They must be very good at hiding the fact that they work or have worked for a chemical company then.
Edit:Is mineral oil of the type used to store solid alkali metals such as sodium,potassium,and lithium suitable for storage of triphosgene crystals?

[Edited on 12-10-2015 by Agari]

Agari - 12-10-2015 at 13:21

Quote: Originally posted by clearly_not_atara  
Quote:
Hmm,that sounds rather interesting, any way to increase phosgene yield for something like that? While I am unlikely to actually be able to prepare those compounds,my initial intended use for the gas was to pipe it over into a concentrated ammonia solution to obtain urea,but I later found out that I would need anhydrous ammonia otherwise most of the gas will be hydrolyzed.
Edit:If I can't increase the yield in any way,I guess I will have to buy a generator from Sigma Aldrich's site.


Orgsyn has a procedure:

http://www.orgsyn.org/demo.aspx?prep=cv5p0201

I suggest an excess of imidazole; better safe than acylated. I (and everyone else here) cannot stress enough the extreme danger you're putting yourself into.

I originally wanted to actually make urea,but now want to synthesize Carbonyldiimidazole.I understand that the other materials that the procedure calls for will be hard to obtain,but if it is a long-term investment,then so be it.

[Edited on 12-10-2015 by Agari]

clearly_not_atara - 12-10-2015 at 15:08

Quote:
Thank you for your rather polite and well-structured comment,good sir.But such manners are too good to be appreciated by plebs such as myself,so I will politely ask you to go fuck yourself.


It's not considered wise to insult senior members of a forum as a n00b, you know.

Maybe try making carbonyl sulfide instead. It can at least be used as a precursor to chloroformates (via thiocarbonates), is generally less toxic, and stinks, so you'll know if you've made a terrible mistake.

http://pubs.acs.org/doi/abs/10.1021/cr50016a002

http://www.researchgate.net/publication/240858232_Non-phosge...

j_sum1 - 12-10-2015 at 15:29

By post 38 you should have figured out that what you propose is not a good idea.
I am going to reiterate that point. I respect the knowledge of those on this board and have a preference for people not dying needlessly.

If you need further explanation as to why it is a bad idea, or (perish the thought) what precautions you should take to make the procedure less hazardous, then just ask. Someone will help.

If this thread degenerates to the level of throwing sand out of the sandbox then that's a problem which will most likely be resolved by sinking this thread into the mire of lame threads on which the sun refuses to shine - aka detritus.

Agari - 12-10-2015 at 15:42

Quote: Originally posted by j_sum1  
By post 38 you should have figured out that what you propose is not a good idea.
I am going to reiterate that point. I respect the knowledge of those on this board and have a preference for people not dying needlessly.

If you need further explanation as to why it is a bad idea, or (perish the thought) what precautions you should take to make the procedure less hazardous, then just ask. Someone will help.

If this thread degenerates to the level of throwing sand out of the sandbox then that's a problem which will most likely be resolved by sinking this thread into the mire of lame threads on which the sun refuses to shine - aka detritus.

Alright,I got a few questions:
What is the best way to store triphosgene crystals,will the type of mineral oil used to store solid alkali metals do the job? How do I know if my gas mask/respirator can block out phosgene?Can you please link a site to purchase one such mask? Finally, let's say I decide to introduce triphosgene crystals to water in a closed system, what is the best way to seal connection points such as those where tubing meets a flask without permanently damaging the glassware?

[Edited on 12-10-2015 by Agari]

softbeard - 12-10-2015 at 17:00

Quote: Originally posted by Aga  

What is the best way to store triphosgene crystals,will the type of mineral oil used to store solid alkali metals do the job? How do I know if my gas mask/respirator can block out phosgene?Can you please link a site to purchase one such mask? Finally, let's say I decide to introduce triphosgene crystals to water in a closed system, what is the best way to seal connection points such as those where tubing meets a flask without permanently damaging the glassware?

[Edited on 12-10-2015 by Agari]


Seriously Agari? You 're planning on 'theoretically' producing, first phosgene, and then triphosgene, and yet you're asking these type of questions?
It's obvious you don't have a clue what you are doing!

Why would you want to store triphosgene under mineral oil? If anything, you need an inert atmosphere like nitrogen or argon.

Anyhow, there's no point in trying to warn you any further about how dangerously stupid your plans sound. Plenty of people on this board have already attempted this.
My only hope is that the worst that will happen is you'll wind up generating some chlorine, while playing around with your TCCA and HCl, that will cause you some mild Cl2 poisoning.
Maybe then you'll be smart enough to realize COCl2, unlike Cl2, won't be considerate enough to give you any clue you've accumulated a lethal dose.
Maybe not; in which case, you'll become yet another posthumous recipient of the Darwin award.

Agari - 12-10-2015 at 18:15

Quote: Originally posted by careysub  
Check out my recent post on the hazard of phosgene, compared to hydrogen cyanide:
http://www.sciencemadness.org/talk/viewthread.php?tid=13590

Phosgene is much more dangerous than hydrogen cyanide due to the fact that phosgene is a cumulative poison, and cyanide isn't.

Phosgene is a very useful reagent, widely used in industry.

But it should only be produced and consumed in a carefully set-up closed system, with provision against any release (an alkali/water solution trap), and with suitable respirator protection (separate air supply, an efficient fume hood, or a mask with a filter known to be effective against phosgene) since accidents happen.

Phosgene has little odor, provides no warning signs, produces no symptoms for up to 48 hours, and once they appear you are already a dead man. There is no treatment.

A phosgene detection badge would be nice also (commercially available).

You can prepare your own with accessible reagents (this is from Sartori's "The War Gases"):
"Method using Dimethyl Amino Benzaldehyde—Diphenylamine
Paper. Phosgene, even if present in traces in the air, can be
detected by means of papers prepared with dimethyl amino
benzaldehyde and diphenylamine.
These papers are prepared by immersing strips of filter paper
in a solution of 5 gm. />-dimethyl-amino-benzaldehyde and 5 gm.
diphenylamine in 100 ml. ethyl alcohol and allowing them to dry
in a dark place, or better still, according to Suchier, in an
atmosphere of carbon dioxide. By exposing these papers, which
are originally white or pale straw-yellow, to an atmosphere
containing phosgene, an orange-yellow colouration is produced in
a few seconds, the intensity of the colour varying with the
concentration of phosgene. This change of colour is also observed
in presence of chlorine or hydrochloric acid.
It is possible to detect phosgene at a concentration of 4 mgm.
per cu. m. of air"

What actually happens that causes the paper to change color when phosgene is present?

Praxichys - 13-10-2015 at 10:03

Quote: Originally posted by softbeard  
Quote: Originally posted by Aga  

What is the best way to store triphosgene crystals,will the type of mineral oil used to store solid alkali metals do the job? How do I know if my gas mask/respirator can block out phosgene?Can you please link a site to purchase one such mask?

Why would you want to store triphosgene under mineral oil?

Especially because it's probably soluble.

@ Agari -

I have an idea. Make some chlorine first. If you can set up your proposed phosgene apparatus (with no reagents) and run a few moles of chlorine through it without smelling any chlorine the whole time then you might be able to pull off diphosgene or triphosgene without killing yourself by accident. While doing it, remember that every whiff of chlorine you smell means that if you were making phosgene, you just killed yourself. You are not allowed to wear a mask, since you need to detect whether you are killing your neighbors by accident.

Remember that you'll need to disassemble and clean out the apparatus as well, using the same rules. While you're doing so, make sure you check for smells in your fume hood exhaust. NDRC 1946 killed a monkey with phosgene with a 1 minute exposure of 145ppm. 10g of phosgene (7ml of liquid or 2.2L of gas) is enough to bring 64000 cubic meters of air to that concentration. Releasing just 10g of phosgene would create a deadly cloud the size of of 26 olympic swimming pools, killing anyone inside within a minute. Diller 1978, studying accidents, determined that death occurs in humans at just 30ppm when exposed for 17 minutes. No bullshit: spilling those 10 grams, assuming the cloud stays <10m high, would kill anyone within 50 meters in 1 minute, and anyone within 100m in 17 minutes. NIOSH puts the "Immediately dangerous to life and health" concentration at 2ppm. This pushes this radius to 360m, or nearly a quarter of a mile. How close do you live to other people?

Do not underestimate the seriousness of the extreme toxicity of phosgene. This is absolutely not suitable for a residential environment.

Agari - 13-10-2015 at 16:54

Quote: Originally posted by aga  
The NSA and/or CIA will be thinking of terms like 'Extreme Rendition' right now.

Any Threat, Foreign or Domestic, wanting to produce deadly gasses with zero idea about their Other uses would automatically be a Target, High Priority, Lethal Force Authorised.

Not having a Target Compound for which you actually NEEDED phosgene will end up being why you're in jail, or inhumed.

Expect a knock at the door soon.

Answer that knock, and make sure you have nothing in either hand, and that both hands are in plain sight or they will kill you.

Is Phosgene sounding less Kewl now ?

I am pretty sure you wrote that because you believe that I have no use for phosgene,yet one of my above posts states that I do indeed plan on using the gas to make Carbonyldiimidazole. Lastly, if we follow your logic,then does that mean that anyone in possession of a level 4 health hazard(NFPA 704) should be getting arrested left,right,and center? Hell, why didn't I get arrested yet?

Agari - 13-10-2015 at 17:01

Quote: Originally posted by Praxichys  
Quote: Originally posted by softbeard  
Quote: Originally posted by Aga  

What is the best way to store triphosgene crystals,will the type of mineral oil used to store solid alkali metals do the job? How do I know if my gas mask/respirator can block out phosgene?Can you please link a site to purchase one such mask?

Why would you want to store triphosgene under mineral oil?

Especially because it's probably soluble.

@ Agari -

I have an idea. Make some chlorine first. If you can set up your proposed phosgene apparatus (with no reagents) and run a few moles of chlorine through it without smelling any chlorine the whole time then you might be able to pull off diphosgene or triphosgene without killing yourself by accident. While doing it, remember that every whiff of chlorine you smell means that if you were making phosgene, you just killed yourself. You are not allowed to wear a mask, since you need to detect whether you are killing your neighbors by accident.

Remember that you'll need to disassemble and clean out the apparatus as well, using the same rules. While you're doing so, make sure you check for smells in your fume hood exhaust. NDRC 1946 killed a monkey with phosgene with a 1 minute exposure of 145ppm. 10g of phosgene (7ml of liquid or 2.2L of gas) is enough to bring 64000 cubic meters of air to that concentration. Releasing just 10g of phosgene would create a deadly cloud the size of of 26 olympic swimming pools, killing anyone inside within a minute. Diller 1978, studying accidents, determined that death occurs in humans at just 30ppm when exposed for 17 minutes. No bullshit: spilling those 10 grams, assuming the cloud stays <10m high, would kill anyone within 50 meters in 1 minute, and anyone within 100m in 17 minutes. NIOSH puts the "Immediately dangerous to life and health" concentration at 2ppm. This pushes this radius to 360m, or nearly a quarter of a mile. How close do you live to other people?

Do not underestimate the seriousness of the extreme toxicity of phosgene. This is absolutely not suitable for a residential environment.


No filters?What about this:
Quote:

A two stage scrubbing system using NaOH/sodium thiosulfate and (separately) KOH/KMnO4 should scrub phosgene, chlorine and carbon monoxide.

?
What about adding that to the apparatus,maybe even having ethanol or ammonia somewhere along the way(separate)?

On a more serious note,can you cite your references?

I live around the area of the Great Lakes(United States), more specifically,Lake Superior, so maybe I COULD in theory move there for the experiment? It would at least remove me from the vicinity of residential areas.Sure,it might be going a bit extreme,but if phosgene is as bad as you say it is,I think it will be worth going there,please see my post about me wanting to make carbonyldiimidazole. Yes,I will actually do it outside instead of under a fume hood,maybe even seal my apparatus completely,even if it means rendering the glassware unusable,assuming COCl2 is as toxic as you say.

[Edited on 14-10-2015 by Agari]

[Edited on 14-10-2015 by Agari]

Agari - 14-10-2015 at 13:41

Quote: Originally posted by careysub  
Check out my recent post on the hazard of phosgene, compared to hydrogen cyanide:
http://www.sciencemadness.org/talk/viewthread.php?tid=13590

Phosgene is much more dangerous than hydrogen cyanide due to the fact that phosgene is a cumulative poison, and cyanide isn't.

Phosgene is a very useful reagent, widely used in industry.

But it should only be produced and consumed in a carefully set-up closed system, with provision against any release (an alkali/water solution trap), and with suitable respirator protection (separate air supply, an efficient fume hood, or a mask with a filter known to be effective against phosgene) since accidents happen.

Phosgene has little odor, provides no warning signs, produces no symptoms for up to 48 hours, and once they appear you are already a dead man. There is no treatment.

A phosgene detection badge would be nice also (commercially available).

You can prepare your own with accessible reagents (this is from Sartori's "The War Gases"):
"Method using Dimethyl Amino Benzaldehyde—Diphenylamine
Paper. Phosgene, even if present in traces in the air, can be
detected by means of papers prepared with dimethyl amino
benzaldehyde and diphenylamine.
These papers are prepared by immersing strips of filter paper
in a solution of 5 gm. />-dimethyl-amino-benzaldehyde and 5 gm.
diphenylamine in 100 ml. ethyl alcohol and allowing them to dry
in a dark place, or better still, according to Suchier, in an
atmosphere of carbon dioxide. By exposing these papers, which
are originally white or pale straw-yellow, to an atmosphere
containing phosgene, an orange-yellow colouration is produced in
a few seconds, the intensity of the colour varying with the
concentration of phosgene. This change of colour is also observed
in presence of chlorine or hydrochloric acid.
It is possible to detect phosgene at a concentration of 4 mgm.
per cu. m. of air"

What actually happens that causes the paper to change color?What reaction occurs?

Praxichys - 16-10-2015 at 10:06

Quote: Originally posted by Agari  

No filters?

If the lethal limit in one minute is 145ppm, and your gas mask filters 99.9% of phosgene, breathing 145000ppm (14.5%) phosgene in air will cause enough to pass the mask filter and kill you in one minute (assuming mask is well-sealed - i.e. you have no facial hair - and ignoring skin and eye exposure). Just 3% outside the mask would kill you in 17 minutes, according to the studies previously cited. Also, the mask filter becomes less effective over time. That time is dependent on how much phosgene it has been exposed to, something unknowable in an outdoor situation.

http://emergency.cdc.gov/agent/phosgene/basics/facts.asp

Can't you buy the carbonyldiimidazole? What do you need it for?

careysub - 16-10-2015 at 10:50

Quote: Originally posted by Agari  
Quote: Originally posted by careysub  
Check out my recent post on the hazard of phosgene, compared to hydrogen cyanide:
http://www.sciencemadness.org/talk/viewthread.php?tid=13590

Phosgene is much more dangerous than hydrogen cyanide due to the fact that phosgene is a cumulative poison, and cyanide isn't.

Phosgene is a very useful reagent, widely used in industry.

But it should only be produced and consumed in a carefully set-up closed system, with provision against any release (an alkali/water solution trap), and with suitable respirator protection (separate air supply, an efficient fume hood, or a mask with a filter known to be effective against phosgene) since accidents happen.

Phosgene has little odor, provides no warning signs, produces no symptoms for up to 48 hours, and once they appear you are already a dead man. There is no treatment.

A phosgene detection badge would be nice also (commercially available).

You can prepare your own with accessible reagents (this is from Sartori's "The War Gases"):
"Method using Dimethyl Amino Benzaldehyde—Diphenylamine
Paper. Phosgene, even if present in traces in the air, can be
detected by means of papers prepared with dimethyl amino
benzaldehyde and diphenylamine.
These papers are prepared by immersing strips of filter paper
in a solution of 5 gm. />-dimethyl-amino-benzaldehyde and 5 gm.
diphenylamine in 100 ml. ethyl alcohol and allowing them to dry
in a dark place, or better still, according to Suchier, in an
atmosphere of carbon dioxide. By exposing these papers, which
are originally white or pale straw-yellow, to an atmosphere
containing phosgene, an orange-yellow colouration is produced in
a few seconds, the intensity of the colour varying with the
concentration of phosgene. This change of colour is also observed
in presence of chlorine or hydrochloric acid.
It is possible to detect phosgene at a concentration of 4 mgm.
per cu. m. of air"

What actually happens that causes the paper to change color?What reaction occurs?


p-DMAB reacts with other reagents form colored dyes. It is used in Ehrlich's reagent for example. It reacts with with amines, pyrroles and indoles forms colorful Schiff base adducts; it reacts with hydrazine to form azo dyes (not an exhaustive list of known color-forming reactions).

I would guess the phosgene reacts to link the p-DMAB with diphenylamine to form a dye molecule, the exact nature of the linkage I do not know (others here can make better guesses about the proper reaction mechanism than me).

Agari - 16-10-2015 at 12:40

Quote: Originally posted by Praxichys  


Can't you buy the carbonyldiimidazole? What do you need it for?


Well,following the same logic,phosgene can also be bought from Sigma Aldrich in solution instead of synthesizing it from triphosgene. As for my possible uses for the (C3H3N2)2CO, I have not gotten any ideas of what I could use it for,but I do know some of the compounds it can be used to synthesize,but I will probably just store the (C3H3N2)2CO until I find use for it.In the meantime,I will hopefully be able to understand the chemistry involved behind the synthesis.
On a sidenote, what contamination could I possibly expect if I run the chlorine generated from the 3 HCl + C3Cl3N3O3 -->3 CNOH + 6 Cl reaction through a test tube filled with sulfuric acid to dry the chlorine during the synthesis of triphosgene?
Edit: How much triphosgene(by mass) would be needed to bring the phosgene concentration to the lethal dose that you described? I want to make sure I don't add too much, assuming that there is a possible leakage even with the NaOH and KOH scrubber in place where possible?

[Edited on 17-10-2015 by Agari]

MeshPL - 17-10-2015 at 07:21

Originally, by mistake, I posted this in a spin-off thread, but anyway...

I have a MAD, but probably bad idea how to make phosgene. Since chlorine condenses at -35C and calcium chloride/ice cooling bath may get you down to -40C you may attempt to liquify chlorine in some way. Dry ice could also be used. Than you could bubble CO through liquid chlorine to make phosgene. Would that react and have at least 1% of not killing anybody?

Agari - 17-10-2015 at 08:11

Quote: Originally posted by MeshPL  
Originally, by mistake, I posted this in a spin-off thread, but anyway...

I have a MAD, but probably bad idea how to make phosgene. Since chlorine condenses at -35C and calcium chloride/ice cooling bath may get you down to -40C you may attempt to liquify chlorine in some way. Dry ice could also be used. Than you could bubble CO through liquid chlorine to make phosgene. Would that react and have at least 1% of not killing anybody?

Could you please link us to the spin-off thread? Industrially,phosgene is produced by running purified carbon monoxide and chlorine gas through a bed of activated carbon.The reaction is typically conducted between 100 and 150 degrees Celsius. If I were to bubble CO through liquid Cl, only trace amounts of phosgene will be produced and would likely result in the yield being insufficient for producing adequate amounts of carbonyldiimidazole,but I could be wrong here.

[Edited on 17-10-2015 by Agari]

Little_Ghost_again - 17-10-2015 at 13:16

no dont link the thread! in one part of this you say you have a need/reason for doing this then later on you say you dont and will store it.
So we dont help druggies but we are allowed to help terrorists?

aga - 17-10-2015 at 13:22

Detritus.

Definitely Detritus.

Increasingly, Dangerous Detritus.

[Edited on 17-10-2015 by aga]

Agari - 17-10-2015 at 13:32

Quote: Originally posted by Little_Ghost_again  
no dont link the thread! in one part of this you say you have a need/reason for doing this then later on you say you dont and will store it.
So we dont help druggies but we are allowed to help terrorists?

You are quite paranoid. How many threads with hazardous/energetic materials actually ended up resulting in intentional deaths? I am pretty sure that the number is 0. I won't try to reply to you again since it will cause the thread to be sent to Detritus.

[Edited on 17-10-2015 by Agari]

aga - 17-10-2015 at 13:42

Detritus is where it should be already.

IF you had an actual Goal, such as make chemical compound X which absolutely required phosgene as a reagent, then this thread would be of some value.

As it is, you appear to want to make a War Gas to kill as many people as possible.

It's not paranoia, just brains still working.

Little_Ghost_again - 17-10-2015 at 17:06

No the reason I dont want it linked is because the other thread has nothing to do with making phosgene.

I am really sorry but you stated at the start you had a reason to make it and gave the reason as making something or other, then a little later you admitted you had no real reason to make it. That makes some pretty jumpy about your intentions, I doubt your a terrorist but all the same you have not be entirely open and honest and want to produce something alot of rational people would not like being made next door to them.

I dont know why this is being allowed seeing as there are so many inconsistent statements you have made, but that is not my call nor any of my business.
But I do find it slightly odd that cooks and kewl get a hard time but you have been allowed to carry on while clearly not being honest about the intent.

Point 1 this started as a theory exercise then became an intent

point 2 you said you wanted to make X or Y, then a few posts on you said you didnt have anything in mind and would keep it untill you had a use for it

point 3 while you live near a remote location, you also intimated that you actually live near people, so if you did make it and tried to store it what would happen if it went wrong and you broke the container or whatever?

Ok I am a noob with absolutely no clout on here, but I am honestly greatful I dont live near you, you come across as if you dont believe how dangerous this stuff is. that alone worries me, if you had some fear and respect for it then I might not have this really bad feeling in my gut.

I am sorry, none of this is personal but you judt dont sound like someone who should be within a 1000 miles of this stuff or anything more dangerous than lego

jnik - 18-10-2015 at 04:36

Quote: Originally posted by Agari  
Is mineral oil of the type used to store solid alkali metals such as sodium,potassium,and lithium suitable for storage of triphosgene crystals?


No. Usual clean and dry plastic bottle (polypropylene one) is good enought. Compound is stable without destruction catalysts (like Fe or charcoal). But you should cover bottle very carefully to reduce probability of leakage. Glass flask is also possible, but plastic is better because of safety reasons. Triphosgene mp is about 80 C, so it is much safer to take a sample just by knoking a bottle with hammer, than melting it up.

Agari - 18-10-2015 at 08:38

Quote: Originally posted by aga  
Detritus is where it should be already.

IF you had an actual Goal, such as make chemical compound X which absolutely required phosgene as a reagent, then this thread would be of some value.

As it is, you appear to want to make a War Gas to kill as many people as possible.

It's not paranoia, just brains still working.


I actually do need phosgene for a compound: carbonyldiimidazole. You either have not read the thread,are trolling, or have not paid attention.

Agari - 18-10-2015 at 08:39

Alright,I will bring up one of my other questions:
What contamination could I expect if I bubble the chlorine through a tube containing sulfuric acid before initiating the synthesis?

Little_Ghost_again - 18-10-2015 at 09:40

Quote: Originally posted by Agari  
Alright,I will bring up one of my other questions:
What contamination could I expect if I bubble the chlorine through a tube containing sulfuric acid before initiating the synthesis?


Dry chlorine

Agari - 18-10-2015 at 10:56

Quote: Originally posted by Little_Ghost_again  
Quote: Originally posted by Agari  
Alright,I will bring up one of my other questions:
What contamination could I expect if I bubble the chlorine through a tube containing sulfuric acid before initiating the synthesis?


Dry chlorine

This is the last time I am replying to one of your posts,I am pretty sure other contamination could result. In one of my other threads under general chemistry titled "Red Material?", I was talking about how I botched the synthesis of SiCl4 and ended up with red material in my product. It turns out that the red substance was sulfur dichloride.

Little_Ghost_again - 18-10-2015 at 11:13

Quote: Originally posted by Agari  
Quote: Originally posted by Little_Ghost_again  
Quote: Originally posted by Agari  
Alright,I will bring up one of my other questions:
What contamination could I expect if I bubble the chlorine through a tube containing sulfuric acid before initiating the synthesis?


Dry chlorine

This is the last time I am replying to one of your posts,I am pretty sure other contamination could result. In one of my other threads under general chemistry titled "Red Material?", I was talking about how I botched the synthesis of SiCl4 and ended up with red material in my product. It turns out that the red substance was sulfur dichloride.


What is your problem?? I gave you an accurate answer the best I could to your question!

What the hell do you think will come through sulphuric acid if you bubble chlorine through it?? It will be dry as the sulphuric will remove the water, so to answer what YOU asked.... if you bubble chlorine though sulphuric acid the other end will give you dry chlorine, I have DONE IT TODAY! I didnt get toads or frogs I got chlorine very dry.

Have a think and see if perhaps YOU might have fucked up the question rather than me fucking up the answer

JJay - 18-10-2015 at 13:28

I certainly have no intention of producing phosgene unless it will make me millions of dollars or lead to a cure for cancer, but hypothetically, if one were to produce phosgene, wouldn't a military surplus gas mask make an ideal respirator?

aga - 18-10-2015 at 14:11

The mods are not interested, so how about Collective Action ?

If nobody posts any more replies, then this thread will die, as it should have, much much earlier.

Helping anyone to make phosgene is simply stupid.

All Stop. Please.

[Edited on 18-10-2015 by aga]

Agari - 18-10-2015 at 16:17

The shipment of reagents has arrived,synthesis will be done tomorrow.

j_sum1 - 18-10-2015 at 16:48

Quote: Originally posted by Agari  
The shipment of reagents has arrived,synthesis will be done tomorrow.

This is the worst news I have heard so far today.
Maybe you have the skills to pull it off but everything you have posted so far causes one to doubt. Critically, you seem to be unaware of the extreme toxicity of this stuff. I am also uncertain that there is any real need to justify this synthesis. You have cited a couple of syntheses for which you need phosgene. Urea for goodness sake! Ok, carbonyldiimidazole also. But again you have not demonstrated any real need that justifies making this via this route.

Several additional things concern me.
The fact that you wish to synthesise a gas that is deadly at such low concentrations and is harmful below its odour threshold is worrying.
The fact that you seem hell-bent on doing this against the advice of everyone who has participated in this thread.
The nature of the questions you have asked suggests that although you might know the reaction itself and the reaction mechanism, you do not appear to have a firm grasp on the details of the experiment setup that are essential to doing it safely. A serious safe attempt would cite others who have done this synthesis, post details of their equipment and invite critique and advice on how to best adapt the procedure for your specific situation.
You mention no contingency plans if something should go wrong. What is your escape plan? What is your containment plan? What is your communication plan? What is your disposal plan? You say that you are doing this away from other people. (How far away, you do not specify. I hope it is far enough.) What do you intend to do with the dead mammals that could potentially occur?

This whole thing smacks of arrogance and irresponsibility. If it was a comparable synthesis of drug-related or energetic compounds the police would be interested. The fact that you are attempting a chemical warfare agent seems to have escaped you. This is just foolhardy.


[edit]
Check in when done so we know you are alive.
Include photos of dead squirrels or pets and their distance from your lab.

[Edited on 19-10-2015 by j_sum1]

careysub - 18-10-2015 at 17:17

A quick refresher on phosgene.

Before the advent of nerve gas it was the number one lethal chemical warfare agent, killing 80% of all those who died of gas in WWI.

Unlike nerve gas, there are no symptoms of exposure (nerve gas at least cause miosis and dim vision that warns of exposure). Even hydrogen cyanide provides some measure of warning if not absorbed too quickly.

Unlike nerve gas or hydrogen cyanide, there is no treatment. Nerve gas can be treated at up to 20 times the lethal dose if intervention is swift - the medicines to treat are readily available. Hydrogen cyanide can likewise be treated with readily available medicines even at high exposures (but its speed of action makes this difficult).

Unlike hydrogen cyanide, phosgene is a cumulative poison that can gradually build up to lethal dose over the course of days through repeated exposure.

And of course it is a gas. It does not stay put.

This is just about the most insidious poison there is.

phlogiston - 18-10-2015 at 17:49

Maybe Agari just craves the attention and doesn't intend to actually synthesize the gas. I fail to understand how someone who is able to come up with a synthetic route is unable to perform such basic planning of a safe setup. It is unbelievable to the point where I think that either his own life has no value to him or he is toying with us.

It is conceivable that he will stop responding to messages in the near future to fake his death, while in reality he will be reading our messages in which we speculate about what happened to him.

If not, I truly hope (for lack of faith in a supernatural being) that Agari is living in an extremely remote area and won't harm anybody but himself.

[Edited on 19-10-2015 by phlogiston]

Agari - 19-10-2015 at 09:18

Moving out in two hours, I will give a status update within the next 72 hours.

Edit:I feel as if I am going to go into cardiac arrest at any moment, I hope I don't F*** this up.

P.S.:The setup that I am going to use not is significantly different from my original proposed setup,I am going to synthesize triphosgene first and then hydrolyze it to phosgene during carbonyldiimidazole synthesis.
To whoever was concerned about my close proximity to others, I don't live in the remotest area possible, but I will drive to a more remote area.
[Edited on 19-10-2015 by Agari]

[Edited on 19-10-2015 by Agari]

Agari - 19-10-2015 at 09:39

Quote: Originally posted by careysub  
A quick refresher on phosgene.

Before the advent of nerve gas it was the number one lethal chemical warfare agent, killing 80% of all those who died of gas in WWI.

Unlike nerve gas, there are no symptoms of exposure (nerve gas at least cause miosis and dim vision that warns of exposure). Even hydrogen cyanide provides some measure of warning if not absorbed too quickly.

Unlike nerve gas or hydrogen cyanide, there is no treatment. Nerve gas can be treated at up to 20 times the lethal dose if intervention is swift - the medicines to treat are readily available. Hydrogen cyanide can likewise be treated with readily available medicines even at high exposures (but its speed of action makes this difficult).

Unlike hydrogen cyanide, phosgene is a cumulative poison that can gradually build up to lethal dose over the course of days through repeated exposure.

And of course it is a gas. It does not stay put.

This is just about the most insidious poison there is.

Nerve agents such as Soman and CycloSarin need to be treated within a VERY short amount of time as neurotransmission is blocked within a matter of minutes,so not ALL nerve agents can be effectively treated even in doses of 20 times the lethal dose.

aga - 19-10-2015 at 12:56

This charade has to End.

Clearly it's an attention-seeking thing, so if members could co-operate (unlikely) then the best course would be either to Not comment further, or comment soley on what the thread IS about rather than the non-existent content.

Funny. I spent 110 mins researching Actors and Web forums, and it apprears that using web forums using multiple personalities helps them hone their 'character acting' skills at no cost to them.

Smart thinking IMHO.

[Edited on 19-10-2015 by aga]

clearly_not_atara - 19-10-2015 at 14:18

Offtopic: Anyone want to buy some land in northern Michigan? I've got 50 acres, recently cleared of all life forms, available starting Wednesday.

Agari - 20-10-2015 at 13:15

Sorry for taking so long to update.
I have finished the synthesis of C7H6N4O,which is now stored in an Erlenmeyer flask under a CO2 atmosphere. The apparatus that I used for the synthesis of phosgene was drastically different from my original proposed idea,though.

Agari - 20-10-2015 at 13:19

I will try to schedule an appointment with a pulmonologist as soon as possible,I am not sure how much time I may have left to live,though I did not have enough phosgene leaking into my mask for me to smell it. COCl2 has a smell like freshly cut grass when present at low concentrations(Data from reading and not from personal experience,Aga), right?

aga - 20-10-2015 at 13:48

Quote: Originally posted by clearly_not_atara  
Offtopic: Anyone want to buy some land in northern Michigan? I've got 50 acres, recently cleared of all life forms, available starting Wednesday.

How much ?

Does it have water and electricity and is there road access ?

Phosgene is a gas, so should have blown away by now.

Does it permeate the soil ?

Looking to put up a hydroponic greenhouse, so soil contamination is no problem, yet should reduce the Price quite a lot i think.

Maybe best to Rent before Buying in case some workers die.

Do you offer a rent-to-buy option ?

phlogiston - 20-10-2015 at 14:12

Does any nasty equipment or stupid dead life forms remain on the plot? What happens if it becomes an EPA superfund site in the future?

Agari, please consider donating your chems, equipment and funds to SM in your remaining time.

aga - 20-10-2015 at 14:37

Hey ! I was here first !

I want the land, the Corpse and all materials in with the deal.

Hate it when these ambulance chasers turn up.

Agari - 20-10-2015 at 17:12

Funny aga,you are telling people to basically send this thread to Detritus,but it doesn't matter now.

Little_Ghost_again - 21-10-2015 at 00:33

Quote: Originally posted by Agari  
Sorry for taking so long to update.
I have finished the synthesis of C7H6N4O,which is now stored in an Erlenmeyer flask under a CO2 atmosphere.


Great write up

And I have pixies sitting under a toadstool

[Edited on 21-10-2015 by Little_Ghost_again]

aga - 21-10-2015 at 09:15

Quote:
but it doesn't matter now.

19-10-2015 at 01:17 says will start tomorrow

20-10-2015 at 22:15 says it's synthed

20-10-2015 at 22:19 says will go to pulmonologist

21-10-2015 at 02:12 still alive and posting

Well, i hope you did Not attempt this stupid and pointless synthesis.

Current Evidence suggests :-

1. you didn't
2. you did and it didn't work
3. you did and it worked

If it's #1, great.
#2 is better than #3, yet still stupid.

Any results of #3 are disasters of your own making despite repeated warnings and urgings to abandon the idea.

Sympathy? I think not.
Quote:
I have pixies sitting under a toadstool

Really ?

Must be the Lesser Striped Central Asian Pixie then, as the Common European Pixie is 9" high and toadstools don't grow big enough.

Little_Ghost_again - 21-10-2015 at 10:17

Quote: Originally posted by aga  
Quote:
but it doesn't matter now.

19-10-2015 at 01:17 says will start tomorrow

20-10-2015 at 22:15 says it's synthed

20-10-2015 at 22:19 says will go to pulmonologist

21-10-2015 at 02:12 still alive and posting

Well, i hope you did Not attempt this stupid and pointless synthesis.

Current Evidence suggests :-

1. you didn't
2. you did and it didn't work
3. you did and it worked

If it's #1, great.
#2 is better than #3, yet still stupid.

Any results of #3 are disasters of your own making despite repeated warnings and urgings to abandon the idea.

Sympathy? I think not.
Quote:
I have pixies sitting under a toadstool

Really ?

Must be the Lesser Striped Central Asian Pixie then, as the Common European Pixie is 9" high and toadstools don't grow big enough.


Might be a mushroom then lol :D

karlos³ - 21-10-2015 at 10:46

As it is autumn, I have seen toadstools that big, might have been a hallucination like OP´s attempted synthesis success?
Who knows? :D

Little_Ghost_again - 21-10-2015 at 12:05

Our wood has some amazing toadstools and mushrooms this year, no idea what half of them are but I will be collecting!
I intend to extract what I can from these and do a TLC, although it looks like finally I may have resolved my problem of getting gas for the GC!!

I like plant extractions but mushrooms and toadstools dont seem to be done as much, I cant find much data on whats in alot of them, the obvious ones are well documented but alot of the normal cant be eaten and dont get you spaced out ones, dont seem to have much on them.

my collection of little centrifuge vials with plant extract samples is growing :D

aga - 21-10-2015 at 12:25

Vials should not Grow. (usually plastic or glass)

Thinking they have grown is an indication that the contents have permeated your mind.

Seems that cubic karlos could help you decide that particular question.

aga - 21-10-2015 at 12:30

@Agari

Let go of this nonsense and start learning some actual Chemistry !

You're still welcome here, despite this opening gambit.

Nicodem - 22-10-2015 at 10:01

I hope you all enjoyed this pathetic waste of time. I'm surprised that so many members have this much time to prolifically reply to trolls. Lucky you, but at least this yielded some good safety related posts here. I doubt there is anything more (of use) to add, so I'm closing this festival.