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Nucleophile
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Extracting Thionyl Chloride form Thionyl Chloride-batteries
Thionyl chloride-lithium batteries contain thionyl chloride (SOCl2). Is it possible to extract it? I know it containes Lithium
Tetrachloroaluminate but a fractional distillation could maybe separate these. I need to find a quick way to synthesise Thionyl chloride but it seems
very hard. The biggest obstacle for me is to use SO3, hence I need to find other ways.'
Any help helps
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HeYBrO
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Why do you want it? if you gave us some more information about the conditions of the reaction you wish to run we may be able to provide a suitable
substitute.
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BromicAcid
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Thionyl chloride batteries can be hard to come across. As far as I can tell though you would not need a fractional distillation, just a flash
distillation should work since lithium tetrachloroaluminate does not appear to be very volatile. Should be just a matter of puncturing a battery,
pulling apart the insides, wringing them out, and seeing what you get. All while wearing proper PPE of course and limiting the duration of time
battery is open before bottle containing the material is sealed (to limit hydrolysis). I would be interested to know how much can be gotten out of a
battery and where you find them. I once bought a H2S personal monitor on eBay, it came and the battery was dead (soldered in place) when I tried to
find a match I found out it was a thionyl chloride type battery but since it was exhausted I figured all the good stuff was used up and disposed of
it. I did once upon a time purchase some SO2/Lithium batteries to recover both reagents. each battery had ~3 grams of sulfur dioxide in them (based
on the gross and tare weights) I found them good to use for reactions since they metered out well. The lithium in those batteries though was just
spooled in the middle so separation was easy (the SO2 just sprayed out).
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Nucleophile
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I needed it to make some acid chlorides as my book described it in the reaction. I worked much on inorganic chemistry so I am not so good in organic
chemsistry. I want to chlorinate an hydroxyl group. (I want to make an acyl halide) The reaction is to make butyryl chloride for making a tertiary
alcohol. I needed SOCL2 , 6ml max)
So the Thionyl chloride has been very big problem to obtain. I tried oxidation of SO2 to yield SO3 on a catayst and reaction with Sulfur chloride but
it was extremely hard to do and it resulted in and accident where i got some minor SO3 burns on my thumb. I wont be trying this approach (SO3+SCL2)
anytime soon. ( I did the reaction at 200 celcius in quartz glass tube)
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HeYBrO
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you can use phosphorus trichloride to make acid chlorides and apparently oxalyl chloride http://www.prepchem.com/synthesis-of-butyryl-chloride/
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hissingnoise
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Yes, using phosphorus trichloride will give phosphorous acid (H3PO3) as byproduct and because it's high-boiling, a good
separation is easy . . .
It's prepared by passing dry chlorine over white phosphorus warmed ina RBF with condenser in an atmosphere of CO2.
The trichloride distills over as it forms!
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woelen
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PCl3 most likely is as hard to obtain as SOCl2. The same is true for white P.
A viable alternative may be cyanuric chloride, (CNCl)3. This must not be confused with TCCA. Cyanuric chloride can be used for chlorination purposes,
itself being converted to cyanuric acid.
Keep in mind that (CNCl)3 is toxic and has a strong smell of mice. It, however, is much easier to handle and store than SOCl2.
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hissingnoise
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| Quote: | | PCl3 most likely is as hard to obtain as SOCl2. The same is true for white P. |
Cyanuric chloride isn't exactly OTC either, woelen . . . ?
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Loptr
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Take this with a grain of salt, because not all of these should be performed, even if you are capable of performing them. Safety should be
taken into account before attempting any of what I have listed below, because your death might be the only major product of these reactions. There was
a member (teenager? maybe) on this site a while back that died from what seems to have either been hydrogen cyanide or phosgene. Please take care, or
find a way of procuring the needed reagents.
It seems bromine is easier to use in these situations in making an acyl bromide than it is to use chlorine to make the acyl chloride, but it typically
proceeds through alpha-bromination for activation of the hydroxyl group, which is then followed by formation of the alpha-bromoacyl bromide. This
might be acceptable. Some acyl halides can be used in the preparation of other acyl halides, so the heavy hitting chlorinating agents might not be
required. Also, the traditional acid chlorides are unavailable for the most part due to CW restrictions, but the bromides aren't listed as far as I
know, so they are more available in general. It depends on the target acyl halide, and is typically due its volatility.
Here is a preparation of acetyl bromide using bromine, acetic acid, and a smallish amount of red phosphorus. The ratio seems to be about 1 part red
phosphorus for every 15 parts of acetic acid, so it sounds somewhat economical. Sulfur could also probably be used instead of red phosphorus, as the
sulfur would form a bromination product that can be used to prepare acyl bromides. I am not the most family with sulfur chemistry, and have seen this
mentioned in papers, so I would advice you to pull it up and see if it is of utility in your situation.
http://www.prepchem.com/synthesis-of-acetyl-bromide/
Another route is through sulfur monochloride using sulfur and dry chloride gas. Here is a preparation of sulfur monochloride on prepchem.
http://www.prepchem.com/synthesis-of-sulfur-monochloride/
Phosgene is a possible alternative, but it has left a collection of bodies in its wake, so make sure you have lots of air flow and PP gear. There are
routes to phosgene from chloroform, carbon tetrahalide, etc., so check out this page for a good listing. There are also related reagents, such as di-
and tri-phosgene that are a liquid and a solid are RT, respectively. I believe that another route is oxidation of chloroform with dichromate.
http://www.prepchem.com/synthesis-of-phosgene/
There is also the possibility of taking an aldehyde to an acyl halide, such as benzaldehyde to benzoyl chloride using chlorine, or toluene to
benzotrichloride, which can be partially hydrolyzed to benzoyl chloride, or simply used on its own as the chlorinating agent. Benzoyl chloride can
also be used to make other acyl chlorides.
There is also a more OTC-friendly preparation of oxalyl chloride available if you search for it, but I have no experience with it or if it works at
all. Others on this forum might be able to better recall the details as I only glanced over the write up, and have no idea where I found it
originally.
Also, you wish to make an acid chloride. What is the target compound? You might be able to make it there using another scheme. If you were trying to
make a better leaving group, ester, etc., there are other viable paths.
A better description of your intention is desirable.
EDIT: Nevermind. You stated the butyryl chloride is to make a tertiary alcohol. There are many ways of making an alcohol, so a literature
search might be in your best interest.
[Edited on 15-4-2016 by Loptr]
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Loptr
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If Sauron were still here he would probably also advice you on the economy of cyanuric trichloride (often written as CC, or TCT) as a solid reagent
for preparing acid chlorides. This is not the same thing as trichloroisocyanuric acid, otherwise commonly referred to as TCCA, TCA, or some
similar acronym that somebody decided to use!!! This can absolutely not be bought in a pool store, as the related TCCA pool shock treatment. There is
also a related compound lacking one chlorine and is the sodium salt of TCCA, known as sodium dichloroisocyanurate, or DCA, and that can't be used
either. I believe that I have read that potassium cyanate can be used to prepare cyanuric trichloride, but again, a search would have to
be performed to confirm my recall.
He was before my time here, and seemed to have a wealth of knowledge of this subject, but as many others, he left for reasons of ego or conflicting
personalities. He also seems to have been older at the time, and if I recall correctly and not just making this up, but I believe I saw a mention in a
post somewhere on here that it was believed he had passed.
EDIT: Someone correct me if I am wrong, but I believe that phosphorus oxychloride (POCl3) can be used in this instance. This can be prepared
by dry distilling phosphorus pentoxide and sodium chloride.
[Edited on 15-4-2016 by Loptr]
[Edited on 15-4-2016 by Loptr]
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Nucleophile
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I am going to syntheisise tert-2-methyl-2-butanol. (from Butryrl bromide I guess. That ampoule of PBr3 that I have bought got 2 months ago from a
chemist in Russia (you would not belive it, (25ml for 4 dollars!!) needs to find some use . I didnt think of it from the beggining as I totaly forgot about it!) Much ''better'' than thionyl chloride.
Thanks for the fast and very informative answers. I think I can do it on my own now!
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Nucleophile
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The phosphorus oxychloride seems very interesting The reaction would be P4O10 + 12NaCL = 4POCl3 + 6Na2O. Howewer this occurs probably around 500
celcius..
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Loptr
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See what I mean about the bromides? You had one in stock and forgot about it.
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Loptr
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Quote: Originally posted by Nucleophile  | | The phosphorus oxychloride seems very interesting The reaction would be P4O10 + 12NaCL = 4POCl3 + 6Na2O. Howewer this occurs probably around 500
celcius.. |
I have never attempted the reaction, nor have I seen a temperature mentioned.
There are other ways to POCl3, apart from the obvious PCl3 route, but I think they are less selective and produce a mixture of products. For instance,
I have read of a procedure involving exposure of phosphorus pentoxide to bone dry HCl until a liquid is formed. POCl3, among other things, can be
distilled from this mixture. I have no reference on hand nor experience with thjis, and would have to look them up to confirm the reaction.
I am a compulsive reader.
[Edited on 15-4-2016 by Loptr]
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BromicAcid
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| Quote: Originally posted by Nucleophile | | The phosphorus oxychloride seems very interesting The reaction would be P4O10 + 12NaCL = 4POCl3 + 6Na2O. Howewer this occurs probably around 500
celcius.. |
Any source for this Loptr? I know you disavowed knowledge of the temperature Nucleophile speculate (which is over the boiling point of P4O10 anyway)
but this does seem like a suspicious reaction if anything. I have seen suspicious reactions work before but their yields are usually abysmally low.
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Loptr
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Len1's book has the procedure and claims a 85% yield from starting P2O5. The temperature starts at 270-300*C, and is complete by 420*C.
https://books.google.com/books?id=VqosZeMjNjEC&lpg=PA170...
[Edited on 15-4-2016 by Loptr]
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Nucleophile
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I am sorry for the giving out the wrong temperature. I was really confused... Thanks for finding the reaction! Ive got P2O5 in abundance (200 grams
is sitting in vacuum desicator).
Is there any good organic chemistry books out there where I can learn from as I want to expand my knowledge in org. chemistry?
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clearly_not_atara
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Can you use an SO3 complex instead of SO3 itself? SO3*dioxane seems like it would work, or at least there shouldn't bee too much reactivity between
SOCl2 and dioxane...
Other oxidizers for SCl2 might exist. NO2 comes to mind. Be aware this is also very toxic.
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Loptr
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I have quite a few on my shelf, but I find myself looking through these two the most.
http://www.amazon.com/Organic-Chemistry-Jonathan-Clayden/dp/...
http://www.amazon.com/Marchs-Advanced-Organic-Chemistry-Mech...
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Loptr
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| Quote: Originally posted by clearly_not_atara | Can you use an SO3 complex instead of SO3 itself? SO3*dioxane seems like it would work, or at least there shouldn't bee too much reactivity between
SOCl2 and dioxane...
Other oxidizers for SCl2 might exist. NO2 comes to mind. Be aware this is also very toxic. |
I apologize if this is something that has been brought up before or happens to be a dead horse (that's been beaten to death, that is). It was a pretty
common reagents on paper, and I used it quite a few times in labs, but I am not the most familiar with its production.
I am not sure if this would be favored in practice, but I spent a few minutes to think about other ways of producing SOCl2 from things other than the
heavy weight contender, SO3, or any of the sulfur halides, which in my own personal experience tend to be pretty anti-social reagents. I don't know if
this will actually work, but here is the balanced equation.
SO2 + 2 Cl2 ---> SOCl2 + Cl2O
The immediate problem is the other major product of the reaction does have explosive tendencies, so you would want to keep it from accumulating in
significant quantities. It is highly soluble in water and exists in an equilibrium with HOCl, and it hydrolyzes slowly enough to be extracted with a
solvent. I have also read that it might potentially be the active chlorinating species involved in water purification, where a chlorinating agent is
used.
If you look further into Cl2O in its potential use (as a solution) in inorganic and organic chemistry, it will react with metal halides to
produce oxychlorides, and is an effective chlorinating agent for side-chain and ring chlorination, but as usual, that depends upon activation.
(there's still the risk of explosion, so....)
Cl2O sounds very useful, but it carries great risk. It has a very low boiling point at 2*C, much lower than thionyl chloride, which is
something like 74*C. I can't get it out of my head that this could be performed in an amateur setting, assuming that accumulation of Cl2O
is kept at a minimum while condensing the SOCl2.
Could someone tell this wannabe chemist why this wouldn't work, because it simply looks too easy on paper and I am sure I am missing
something.
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Nucleophile
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What wannabe chemist?
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Loptr
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Me. lol I was adding to the post along the same lines as the other post above, about a possible alternate route to SOCl2.
I was going out on a branch with something I had no references for asking if it would be favorable, crazy to attempt, or it was completely without
basis.
I was placing the responsibility on others to confirm my thoughts before attempting to do so myself. Not to mention that I have done work in the
computational chemistry/physics field, all the while wishing I could do the bench work, hence, the wannabe chemist. I no longer am in that field, and
another reason for the name.
[Edited on 16-4-2016 by Loptr]
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Nucleophile
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Loptr, what do you think of this method then?
Reaction of Cl2O with S? I've have read it somewhere (5 years ago) but I can't remember any of the details. As soon you mentioned Chlorine monoxide I
remembered this reaction. I think this is rather explosive because Cl2O is very strong oxidiser and sulfur is, you guessed it..
Preparation of chlorine monoxide
Chlorine monoxide is product in the reaction of chlorine gas with hydrated sodium carbonate, at 20-30°C.
2 Cl2 + 2 Na2CO3 + H2O → Cl2O + 2 NaHCO3 + 2 NaCl
Then drying the gas through silica and leading the gas into molten sulfur the same way you make S2Cl2. However using small quantities of Cl2O at the
time decreases the chance of explosion as thre is much less oxidiser.
Sulfur melts at about 115 degrees Celsius, and the Cl2O decomposes explosive into Cl2 and O2 at temperatures around 120 degrees Celsius. Thats a
small temperature difference.
This reaction just sat in my head (I read it somewhere...) so I don't have any basis if it works or not. Tell me what do you think
PS, sorry for my short and not so informative posts. I'm Swedish and learning English
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Loptr
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I have since found this to be discussed here already.
Here is a link to a post by AJKOER.
http://www.sciencemadness.org/talk/viewthread.php?tid=23152
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clearly_not_atara
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The essential fact to be remembered ia that Cl2O is both very unstable and very reactive. It thus isn't likely to be a favored elimination product
from SO2Cl2 + Cl2. Likewise if you oxidize S with Cl2O you might get S + Cl2O >> SOCl2 but you'll also get SOCl2 + 2Cl2O >> SO3 + 3Cl2.
Chlorine suboxide is to be compared to ClF3 or F2O as a very reactive motherfucking compound. ClO2 is more stable, but its reactions tend to be so
exothermic they cause it to decompose violently.
You might be able to reduce SO2Cl2 with something sufficiently oxygen-loving, eg:
SO2Cl2 + SbCl3 >> SOCl2 + "SbOCl3"
SO2Cl2 + SnCl2 >> SOCl2 + "SnOCl2"
SO2Cl2 + PbCl2 >> SOCl2 + "PbOCl2"
The fourth reaction sounds promising. Lead (IV) chloride isn't very stable. Otherwise I think NO2 is definitely the best candidate for oxidizing SCl2
unless someone has a better idea.
[Edited on 17-4-2016 by clearly_not_atara]
[Edited on 17-4-2016 by clearly_not_atara]
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