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Sauron
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TCCA 50 Kg, What to Do with It? Haven't got a Pool!
I finally got around to locating TCCA in Bangkok.
It's sold by a pool & spa supplies company, Nissan brand "TCCA-90" in 50 Kg packaging for less than $4 US a Kg. When the 7% VAT is figured in,
just under $4/Kg at the present miserable exchange rate.
So I ordered 50 Kg (110 lbs). A lifetime supply for me, most likely.
They also sell the sodium dichloroisocyanuric acid, and "isocyanuric acid" most likely cyanuric acid itself, I reckon. But I have no great need for
the sodium sailt, and when I use the TCCA I'll be left with the CA anyway, which can be regenerated to TCCA. However that takes Cl2 and as I plan to
generate Cl2 from TCCA, that is a wee bit circular. Also with 110 lbs at hand I doubt that regeration will be an issue.
[Edited on 1-4-2008 by Sauron]
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woelen
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The price for your TCCA is quite good, but I would not want so much of the stuff around. Isn't its shelf life limited? I have a 1 kg bottle of the
stuff and I paid EUR 16 for that, it must be pure TCCA, the package tells me that it has 92% active chlorine in it.
Funny to read your low price though. This nicely shows how many times the price rolls over before the stuff is in the hands of the end-consumer.
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Sauron
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Acros wants $56/Kg for this. By the time their products are delivered to me, double that. So if I only use 2 Kg out of this drum or whatever, I will
have broken even.
Anyway what is left behind is CA which I can utilize somehow.
The usual "retail" packing is 10-20 Kg and at a higher price per Kg, so, this is not so bad.
I may repack it into smaller container which may help with the shelf life.
It is now time for me to start planning the utilization of this. One use is to generate Cl2. I know a lot of things I can use Cl2 for.
Another is oxidation of secondary and benzilic hydroxyls to carbonyls. But I already have this covered, using PVPCC (PCC on solid support.)
I know about oxidizing THF to GBL, in which I am scarcely interested.
What ELSE can I do with this drum of powdered TCCA before it turns into cyanuric acid?
[Edited on 1-4-2008 by Sauron]
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woelen
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You can use it to make chloroform from acetone and NaOH. This requires a good distillation setup though, but I am quite sure that is not a problem for
you. Garage chemist has a good write-up on this. It may not be the easiest way and most efficient way of making chloroform, but if you have sooooo
much of this stuff, then efficiency is not your primary concern.
Maybe you could resell this in smaller lots through eBay. There may be other home chemists in your area, who might be happy with 1 kg of TCCA, even if
it costs them $20 for the material + shipping.
[Edited on 31-3-08 by woelen]
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CyrusGrey
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Thats alot of TCCA! I have one puck of it thats about 200g. When I bought it in the store it came it a little sealed plastic bag which hasn't been
opened yet. At that time the bag was about the same size as the puck, now that I am storing it outside in a warm environment it has fully inflated! It
gasses off enough chlorine that the bag is firm because of the pressure inside of it.
Make sure you don't store it near any metal or even plastic that you care about. When I worked at the pool store that I bought my TCCA from, people
would bring in pool cleaners for us to repair. Every once in awhile they would bring in one that they stored next to their bucket of TCCA. The plastic
would be fractured across the whole cleaner, the outside would be covered in a fine layer of powder, and all the chemical resistant screws would be
covered in a thick layer of rust. These cleaners are meant to be resistant to chlorine and hypochlorites that are in the pool water.
[Edited on 31-3-2008 by CyrusGrey]
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Sauron
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They gave me a choice between granular and powdered. I chose the latter, reasoning I'd likely have to waste time powdering granules otherwise.
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Klute
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Please let me know if you try using it for oxidations of alcohols. I've put quite some effort into such reactions myself a few months ago. I got mixed
results, depending on the substrates. Don't use acetone without excess base though, i got some product contaminated with chloroacetone even after naoh
washes, that wasn't too pleasant :S.
I think using a TEMPO-derivative catalyst would greatly help here. I've still not processed my triacetoneamine for 4-OH-TEMPO yet...
Oh, im sure you'll find loads of things to do with it. I imagine you have read the "versatil reagent" review that was uploaded here. Hum, it could
actually be you that posted when i think of it...
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Sauron
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I've also seen reactions attributed to TCCA in the literature that upon a closer look, were done with TCT. These acronyms get a lot of people in
trouble.
My files on TCCA are on another machine, I will have to go and review.
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CyrusGrey
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| Quote: |
Another is oxidation of secondary and benzilic hydroxyls to carbonyls. But I already have this covered, using PVPCC (PCC on solid support.)
I know about oxidizing THF to GBL, in which I am scarcely interested.
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Good point about the acronyms! 
| Quote: |
I've also seen reactions attributed to TCCA in the literature that upon a closer look, were done with TCT. |
What is TCT? I would ask about the others too, but they sound organicky, and I haven't studied much organic chem yet.
I only knew TCCA because I used to sell it.
[Edited on 31-3-2008 by CyrusGrey]
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The_Davster
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As a use for the cyanuric acid byproduct of whatever you use the TCCA for, do you have any uses for calcium cyanamide?
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Sauron
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TCT is Cyanuric Chloride CC Trichloro-s-triazine C3N3Cl3 the acid chloride of cyanuric acid. The Cl atoms are arrached to carbon.
TCCA is trichloroisocyanuric acid.
In TCCA the Cl atoms are attached to Nitrogen, the carbons are all carbonyls. C2N3Cl3O3
TCT is useful for chlorinating alcohols and preparing acyl chlorides.
TCCA is useful as a Cl2 source and as an oxidizer (ethers to esters, secondary alcohols to ketones etc.)
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garage chemist
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You can dissolve it in NaOH solution to make fresh NaOCl without using chlorine gas, I think it forms trisodium cyanurate as the byproduct. So 6 mol
NaOH would react with 1 mol TCCA to give 3 mol NaOCl.
Adding acetone then gives chloroform, I did that once.
With all the chlorine you can make with it, you can chlorinate carbon disulfide to get CCl4 or, in two steps, thiophosgene.
Chlorinate methyl formate to diphosgene, or dimethyl carbonate to triphosgene.
Or make actual phosgene, either from CCl4 and Oleum or CO and Cl2.
Make sulfuryl chloride from SO2 and Cl2 with charcoal or camphor as catalyst- useful for organic chlorinations, and possibly as a chlorinating agent
to make acyl chlorides or anhydrides from salts. I don't have any information about that though.
Liquefy chlorine with dry ice and fill it into a steel cylinder. I've always wanted to do that, but never trusted my gas drying capabilities enough
(only absolutely dry chlorine is unreactive towards steel).
Make volatile metal chlorides, like TiCl4 (I will soon do that myself, need it for Ti(OBu)4. I purchased 500g titanium sponge for it.), SnCl4,
SbCl3/SbCl5, SiCl4, AsCl3, BCl3.
Anhydrous sublimed ZnCl2 and FeCl3. NbCl5- this one catalyzes acetylene trimerization.
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Sauron
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Thanks. I have a long list of things to do with Cl2, but a much shorter list of other things to do with TCCA.
Very good to know that procedure for NaOCl. Well cooled I assume.
I think first procedure will be to chlorinate ethanol to chloral and explore what I can make out of that.
Preliminary: 1 Kg TCCA is a bit more than 4 mols so requires 12 mols HCl to make 12 mols molecular Cl2. Conc HCl is 10.2 M so 1200 ml will give a
slight excess - I understand the yield of Cl2 is about 90-93% of theory. I can clean up this rough calculation later.
C3N3O3Cl3 + 3 HCl -> C3(NH)3O3 + 3 Cl2
and of course the water that HCl was dissolved in remains behind.
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Maya
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<<<<< What ELSE can I do with this drum of powdered TCCA before it turns into cyanuric acid? >>>>
Is that a one way rxn, or is it reversible with excess Cl2 at higher pressure or temp. etc?
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YT2095
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I use NaDCC and TCCA in Beer brewing and jars for Preserves and chili sauce etc... as it makes a great glass steriliser, perhaps you sell some to a
small local business that does this sort of thing too?
aha, another Idea just popped into my head, how about a Maternity ward at a charity hospital!
they clean baby feeding bottles all the time, and that`s what they use, in fact my NaDCC is baby bottle steriliser tablets 
[Edited on 1-4-2008 by YT2095]
\"In a world full of wonders mankind has managed to invent boredom\" - Death
Twinkies don\'t have a shelf life. They have a half-life! -Caine (a friend of mine)
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Sauron
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I'm not trying to sell it or give it away but to put it to use myself.
Anyway making chloroform will consume quite a bit. Making Cl2 will as well.
Maya, I know it turns into cyanuric acid, and that it can be regenerated but that takes a Cl2 source and this stuff IS my Cl2 source. So that is
circular.
Doubtless I can exploit the CA somehow. Cyanamides have been mentioned.
[Edited on 1-4-2008 by Sauron]
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MagicJigPipe
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"I think first procedure will be to chlorinate ethanol to chloral and explore what I can make out of that."
I often wondered if chloral could be made with TCCA. Unfortunately, I'd rather not risk it as chloral hydrate is a CIV controlled substance in the US
and surely a detectable level of it will be produced in the process.
EDIT
It has been brought to my attention that it seems like I wanted to talk about drugs. However, I had no such intent. I was just expressing my concern
about producing chloral in the US. I was hoping someone would alleviate my fears.
A quick search of the site through google turned up little information of chloral synthesis via TCCA in situ. Am I missing something or has this not
been discussed?
[Edited on 1-4-2008 by MagicJigPipe]
"There must be no barriers to freedom of inquiry ... There is no place for dogma in science. The scientist is free, and must be free to ask any
question, to doubt any assertion, to seek for any evidence, to correct any errors. ... We know that the only way to avoid error is to detect it and
that the only way to detect it is to be free to inquire. And we know that as long as men are free to ask what they must, free to say what they think,
free to think what they will, freedom can never be lost, and science can never regress." -J. Robert Oppenheimer
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Sauron
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I'm not in the US, chloral is simply a reagent as far as I am concerned and if you don't believe me, have a look in Chemical Reviews.
Please stick to chemistry in this thread. I am bored to tears with drug discussions.
Org.Syn. includes maybe 6-8 preps that employ chloral or chloral hydrate as starting material
Trichloroethanol
Dichloroacetamide
Dichloroacetic acid
Isatin
to name a few off the top of my head.
[Edited on 2-4-2008 by Sauron]
Attachment: cr60295a001.pdf (1MB)
This file has been downloaded 794 times
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Sauron
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Anyway here's something much more interesting.
TCCA oxidizes ethers with at least one methylene group adjacent to the O, to esters. The carbonyl group goes on the methylene.
R-CH2-O-R'
Thus Et2) gives ethyl acetate 49% -so far this is boring because who wants to make EtOAc out of Et2O, we'd rather the reverse, and the yield is
indifferent.
n-Bu2O, 100% yield of butyl butyrate. More interesting, a boring product but a clean quantitative reaction is always interesting.
Benzyl ethyl ether gives benzaldehyde 52% and a small amount of ethyl benzoate.
Benzyl alcohol and TCCA gives same yield of benzaldehyde.
So I go to wondering, how about a symmetrical ethylene glycol ether like 1,2-dimethoxyethane (monoglyme), a common solvent.
Most likely this gives methyl methoxyglycolate.
Not dimethyl oxalate unfortunately. For the same reason that Et2O does not give Ac2) at least not with this reagent.
This reaction of TCCA is probably best known for its application to cyclic ethers, particularly THF which gives GBL (gamma-butyrolactone.)
p-Dioxane ought to give the cyclic ester of glycollic acid.
I wonder if phenetole gives phenyl acetate?
[Edited on 2-4-2008 by Sauron]
Attachment: tl1968[1].pdf (89kB)
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chloric1
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For Cl2 production, I prefer NaDCCA as it dissolves in water to a measurable degree and when you add 32% HCl with stirring you get a more consistent
reaction although there is foaming and the increasing production of insoluble cyanurates with continued HCl addition which make reaction a little more
sluggish.
Fellow molecular manipulator
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Sauron
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There seems to be some diversity of opinion about TCCA vs NaDCCA. I am relying on len1 and garage chemist. NaDCCA is available from same supplier in
same packing. Obviously, NaDCCA delivers less Cl2 per mol and less Cl2 per Kg. c.40% less. I do not have a price for NaDCCA though I can get it
easily enough.
I base my top of the head 40% less Cl2 estimate on:
2 Cl vs 3
2. Higher MW due to Na and O. So fewer mols/Kg.
TCCA reacts with conc HCl is solid phase; it is insoluble in water and so is the CA produces. Len1 reports stirring is not required, and heat is not
produced. So, conc HCl is dripped onto TCCA powder Cl2 evolves. Water and CA accumulate. I reckon 1 Kg TCCA calls for 1200 ml (approx) conc HCl and
about a 90% yield of theoretically a little more than 12 mols Cl2 is produced. A conc H2SO4 drying train is employed to dry the Cl2. Len1 reported
only about 1% water. A final bottle of P2O5 would give absolutely dry Cl2.
The slightly acid watery sludge of CA is washed out of the generator with warm water, filtered, washed free of HCl and dried.
I have a number of 10 L glass bottles with GL45 mouths and PTFE lined caps. I think I will use these to repack the TCCA and store them in a cool dark
place.
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woelen
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Be careful with storing TCCA, Na-DCCA and hypochlorites in a completely sealed bottle. I noticed buildup of pressure, each time I open the cap, I hear
a hissing sound.
What I have done now is using a cap, in which I have made a very small hole with a hot needle. On this hole, I have put some adhesive tape. So, if
pressure is built up, then the tape is pressed out, but if pressure decreases (due to thermal cycling, cooling down), then the tape sticks to the
little hole and the bottle is closed again. This works fine for me.
Making chlorine works best from TCCA to my opinion. With Na-DCCA and Ca(ClO)2 the production of chlorine is very fast and you need to regulate the
flow of HCl. With TCCA you simply can add a lot of HCl and then chlorine is released at a fairly constant rate.
Recovering the CA after usage is a little more involved than simply rinsing, filtering and drying. I have noticed that small amounts of TCCA remain
trapped in the sludge (smell of chlorine in the dry product). So, what I do is heating the liquid and adding as little as possible water, but enough
for dissolving all of the TCCA+CA in the boiling liquid and expel any chlorine. Then I let it cool down slowly. This results in crystals of CA, which
also are easier to separate than some fine sludge.
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Sauron
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Thanks, woelen. Nice tips. So your advice is to just add the stoichiometric amount of conc HCl to TCCA at the start and let it go at that? You concurr
with len1 that stirring is unnecessary?
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Jor
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one reaction where Na-DCCA would be preferred is the chemiluminiscense with hydrogen peroxide. Woelen made a beautiful webpage about it.
http://81.207.88.128/science/chem/exps/chemlum/index.html
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Klute
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Sauron, wouldn't passing Cl2 over P2O5 produce some POCl3 or other chlorinated phosphorus compounds?
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