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Author: Subject: phosphorus oxychloride (POCl3)
Slimz
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[*] posted on 9-10-2007 at 09:00
phosphorus oxychloride (POCl3)


I have searched thru and researched some. This Chemical is scheduel 3 so i should be able to get my hands on this correct?

I UTFSE and found info about SOCl2 (Thionyl chloride), but not so much about POCl3. Is this used in high quantities in any consumer products. Is it possible to synthesize this at "home".

If there are threads already that I have missed, just post em here and ill check em out, I never have much luck with that search engine.

**Bonus**
in my searching i found an interesting link
http://www.roguesci.org/megalomania/synthesis.html


[Edited on 9-10-2007 by Slimz]
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Phosphor-ing
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[*] posted on 9-10-2007 at 09:33


Search through Google. The search string should include "site:sciencemadness.org" without quotes.
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[*] posted on 9-10-2007 at 09:46


I did that and came up blank.



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[*] posted on 9-10-2007 at 12:58


Google returns hundreds of hits from this site containing "phosphorus oxychloride" or "pocl3." No consumer product contains it and I'm not aware of any really "easy" synthesis. All lab procedures that I've seen start from PCl3 or PCl5. Those materials are not markedly more available than POCl3 itself. The chlorides are prepared in the lab from elemental phosphorus, which can be produced in a home lab but not easily.



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Slimz
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[*] posted on 9-10-2007 at 14:03


ok so i could obtain POCl3 thru hydrolysis of PCl5
PCl5 + H2O → POCl3(phosphorus oxychloride ) + 2 HCl(dichlorobenzidine)

You mentioned that PCl5 was more available?

[Edited on 9-10-2007 by Slimz]




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[*] posted on 9-10-2007 at 15:43


Kindly elucidate why you want POCl3 and/or SOCl2.

Whose "schedule 3" are you referring to?

If you want to make acid chlorides, there are better reagents that are not politically incorrect.

But I doubt that you even know what an acid chloride is, so what is your game?




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[*] posted on 9-10-2007 at 17:30


Souron

#1 Im interested in dehydration of primary amides
#2 Schedule 3 substances, in the sense of the Chemical Weapons Convention
#3 I was not asking about any specific reactaions
#4 Acyl chloride is more proper and i do know what one is.

FYI i have spent alot of time reading and cross refrencing this past week and hav e come here with a very specific question/request. My motives are intelectual. I am not experienced enough to atemt any of the complex (or in some case simple) reactions, nor handle the toxic and dangerous chemicals, that would be needed to atempt the specific synthesises that you seem to be implying that im iterested in. I can understand your concern, but im not stupid enough to actualy try to manufacture a drug. It would be cheaper and easier to buy it anyway.




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[*] posted on 10-10-2007 at 05:31


It's a forum. All members are free to post in any thread. It's not "your" thread. It's Polverone's thread.

As to your personal attacks, I will let the moderators deal with them and you.




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[*] posted on 10-10-2007 at 11:01


All members are free to post on-topic information in every thread. I had to prune a lot of trash from this thread because that rule was somehow forgotten.

Slimz, I was saying earlier that PCl5 is not easy to get. There is no easy way to get POCl3 in a home lab without purchasing some pretty restricted materials*. Any route from OTC materials is going to be very difficult and involved.

*Sauron said this in an earlier post that I had to delete because of much unrelated off-topic content. You might not have believed him. He was right.




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[*] posted on 25-10-2007 at 15:58


There's usually ways around something if you want there to be. If someone really wanted POCl3, they could make it in the usual way from PCl3 (i.e. from the less restricted dichlorophenylphosphine + AlCl3), for instance. You just have to look.
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[*] posted on 25-10-2007 at 16:47


I think that compound is also called "phosphoryl chloride", or "phosphoryl trichloride" or "phorsphoryl(V) trichloride", or similar. Look for it under these names.
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[*] posted on 25-10-2007 at 19:40


It all depends on where you live and what your status is with the suppliers. I can get SOCl2, POCl3 and a lot of other "restricted" things. I have a long standing status as a business that uses these things from time to time. I had as much trouble with CCl4. I favor TCT since Sauron acquainted me with it. Do a search for those threads where its use is illucidated. Hint- username-Sauron; subject line - TCT. BTW a few typos are one thing but we all might undertand you better if you ran your posts through a spell-check. Just a suggestion.

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[*] posted on 12-8-2008 at 13:01
Easy synthesis of POCl3


I've been devouring the phosphorus chapter in J. W. Mellor's "Comprehensive treatise on inorganic and theoretical chemistry" (Vol. VIII), which provided me with the following procedure for synthesizing phosphoryl chloride:

"When P2O5 is saturated with dry HCl, it becomes liquid, and the liquid, on distillation, gives off POCl3, and leaves a residue of HPO3." (p. 944)

and

"(...) when P2O5 is heated (...) with NaCl, POCl3 is formed (...)" (p. 945)

If you're not in the possession of any P2O5, the same reference says:

"When Ca3(PO4)2 is heated with finely divided SiO2, CaSiO3 and P2O5 are produced." (p. 742)

The latter procedure is similar to the industrial (and historical) synthesis of phosphorus (and a constituent part of that process), as described in the phosphorus thread:

http://www.sciencemadness.org/talk/viewthread.php?tid=65

Also:

"The composition of bone-ash may be taken to be P2O5 39.5%, CaO 52.5% (...)" (p. 735)

Now turn the calcium compounds to something that doesn't react with the POCl3 on formation, and use the mix in one of the first couple procedures.

[Edited on 12-8-2008 by jarynth]
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[*] posted on 12-8-2008 at 13:38


Quote:
Originally posted by Sauron

Whose "schedule 3" are you referring to?



This one: http://www.cbwinfo.com/Chemical/Precursors/p2.shtml




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[*] posted on 12-8-2008 at 14:59


Quote:

"When P2O5 is saturated with dry HCl, it becomes liquid, and the liquid, on distillation, gives off POCl3, and leaves a residue of HPO3." (p. 944)


Yes that might be a neat trick but try heating calcium phosphate mixed with carbon in a combustion tube heated to 750 Celsius and run dry Chlorine throught the heated mix. A mixture of products should come over incuding POCl3. Just redistill to purify.

Another path would be converting calcium phosphate to phosphide with aluminum powder or carbon and heat the phosphide in dry chlorine at 100 Celsius to make PCl3. This can be oxidized to the oxychloride with potassium chlorate.




[Edited on 8/12/2008 by chloric1]




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[*] posted on 12-8-2008 at 17:13


Mellor is pretty useless preparatively, he is short on details, where the devil resides.

The calcium phosphate method is an old commercial one starting from rock phospahate. Lots of patents on it.

The reaction between NaCl and P2O5 works fine, if you happen to have an autoclave (pressure reactor.) You can't do it in glass. You can find the experimental details in a JACS article by a fellow named Tarbutton in 1940. Oh, the P2O5 and NaCl must be scrupulously dry because any moisture present ends up reducing the yield and turning into HCl.

The one about saturating P2O5 with dry HCl - well to try it you'd need a tank of anhydrous HCl, and an apparatus bone dry and charged with P2O5 and utterly isolated from atmospheric moisture. You could achieve that with dry Argon, but not N2 because N2 is not inert to P compounds, P-N bonds form. I guess if you go to all that trouble then you will find out if P2O5 liquifies under dry HCl. But I'd recommend you continue passing in HCl. That's because my recollection is that POCl3 (putatively forming and dissolving the rest of the P2O5) reacts with P2O5 and so you have a couple of competing reactions going on and you want to drive them toward POCl3 as primary product.

It would help to have some equations for those reactions.

I know of one other reaction of P2O5 that yields POCl3, the only other products being CO and CO2. But the reagent is not cheap. The same reagent will convert As2O3 to AsCl3. It'll convert antimony and bismuth oxides (corresponding to anhydrides) to the respective chlorides. If P2O3 were available it would convert that to PCl3. The reason why the use of this reagent to convert P2O5 to POCl3 is rarely mentioned is because the reagent is made from PCl5 and so is POCl3 so in that light there's little point. The reagent is oxalyl chloride. The reactions I am talking about were all detailed by Roger Adams in JACS prior to 1920.

So, one not so easy industrial route.

One easy but requiring an expensive steel autoclave.

One easy but requiring a costly reagent.($600 a liter and rising.)

You can still scrape red P off tens of thousands of striker strips and make PCl5, then hydrolyze that to POCl3. But I would not call that easy.




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[*] posted on 12-8-2008 at 17:26


Hum, it's a pity the NaCl/P2O5 would haev been a very neat preparation, both easily obtained and can be easily dried (NaCl). large amoutns of HCl is somethign else, and if generated at home, would require very scrupulous drying, surely wasting alot of P2O5 in a inline drier...

I would think anyone that can get oxalyl chloride can get POCl3, no? It's way cheaper...




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[*] posted on 12-8-2008 at 18:37


POCl3 is way cheaper, but here, it's restricted while oxalyl chloride is not.

And in my case, I do have a heated and stirred autoclave, with a working capacity of 650 ml. So I can try the NaCl route as well. The pressure is autogenous. Temperature 300 C. so obviously the POCl3 is in vapor phase till the reactor cools. A minor ampount of PCl3 also forms, I'd like to figure out how to make that the major or only product. Tarbutton theorized catalytic action of Fe from the autoclave walls.

The reason why glass is unusable is, molten P2O5 just like hot phosphoric acid will eat glass. The reaction takes the better part of 24 hours, plenty time to trash a flask.

See the Tarbutton paper, which was principally about POF3 but also illustrated POCl3.

Beats the hell out of matchbook striker strips.




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[*] posted on 24-12-2011 at 12:22


Preparation of phosphorus oxychloride
(Phosphoryl chloride, Phosphoryl trichloride, Phosphorus trichloride oxide, Phosphoric trichloride, )

1,
3 PCl3 + KClO3 = 3 POCl3 + KCl
(Dervin, C. r. 97. 576)

2,
3 PCl5 + 3 P2O5 = 5 POCl3
(Kolbe und Lautemann, A. 113, 240)

3,
PCl5 + H2O = POCl3 + 2 HCl
(Wurtz, Ann. chim. [3] 20, 472, 1847)

4,
Ca2P2O8 + 2CO + 4Cl = CaP2O6 + 2 CO2 + 2 CaCl2
CaP2O6 + 4CO + 8Cl = 2 POCl3 + 4 CO2 + CaCl2
(Riban, C. r. 95, 1161, 1882)

5,
2 H3BO3 + 3PCl3 = B2O3 + 3 PClO3 + 6HCl
(C. Gerhardt, Ann. Chim. Phys. [3] 45, 90-107 (102 Fubnote 2), 1855)

Attachment: E. Dervin Compt. Rend. 97, 576 ,1884.pdf (144kB)
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Attachment: Riban, C. r. 95, 1161, 1882.pdf (231kB)
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Attachment: C. Gerhardt, Ann. Chim. Phys. [3] 45, 90-107 (102 Fubnote 2), 1855.pdf (120kB)
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[Edited on 24-12-2011 by Mush]
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[*] posted on 24-12-2011 at 13:26


1,
2CrO2Cl2 + 4PCl5 = 4POCl3 + 2CrCl3 + 3Cl2
(H. SCHIFF , Liebigs Ann. Chem. 102 [1857] 111/8, 118))

2,
3 PCl3 + NaClO3 = 3 POCl3 + NaCl
( Ber. 34, 650 [1901])

3,
3 PCl3 + KClO3 = 3 POCl3 + KCl
(Ber. 34 (1901) 2172)

Attachment: Ber. 34 (1901) 2172 Ueber die Herstellung des Phosphoroxychlorides .pdf (117kB)
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Attachment: H. SCHIFF (Liebigs Ann. Chem. 102 [1857] p 111 (p118)) .pdf (357kB)
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