Sciencemadness Discussion Board

making SCl2 From TCCA-Na2S,possible or not?

halogenstruck - 1-4-2010 at 10:54

is it possible to make SCl2 by this method
or just results in other products?
i sorrily don`t` have chemicals to do experiments here.

Na2S+2TCCA==high boiling point neutral solvent==reflux==>SCl2 ?
Na2S2+2TCCA==high boiling point neutral solvent==reflux==>S2Cl2 ?

or just NaSCNO+NaCl??

Picric-A - 1-4-2010 at 11:13

I guess it would just make a mess as there are several possiblities of this reaction,
eg- TCCA + H2O --> CA + HOCl
Na2S + H2O--> H2S + NaOH ect....

halogenstruck - 1-4-2010 at 12:00

actually i mean in dry solvent and dry conditions.
anhydrous Na2S too
there should not be any water.
Ideal reaction would be like this:
2C3Cl3N3O3+3Na2S(anhydrous)=??=>6NaCNO+3SCl2
can someone experiment it as it can be a very promising procursor for SOCl2,PCl3,...

[Edited on 1-4-2010 by halogenstruck]

Taoiseach - 1-4-2010 at 12:16

Well SCl2 is volatile while the sodium cyanurates are not... its definetely worth a try! The problem is... there's primary secondary and tertiary isocyanurates... little information is available on their properties. There's no way to predict a possible outcome of this reaction other than to try it IMHO :)

Picric-A - 2-4-2010 at 04:16

halogenstruck - How are you assuming sodium cyanurate and sulphur dichloride will form? do you any references?
If you do it in a non aqeous solvent the chances are the Na2S will not be soluble. Acetone might be a good substitute and IF the reaction you mention does work you would co-distill acetone and SCl2.

Sauron - 2-4-2010 at 06:11

Make Cl2 from TCCA and run it into molten sulfur.

Brauer teaches how to isolate SCl2 from S2Cl2 at least temporarily.

halogenstruck - 2-4-2010 at 06:25

reacting S&Cl2 is standard method but if aforementioned route works,it`s a good idea for easier and larger scale production without involving with chlorine gas

Sauron - 2-4-2010 at 12:44

Ever snell SCl2?

It's a lot nastier than Cl2.

JohnWW - 2-4-2010 at 13:11

SCl2 is likely to be at least as poisonous as H2S, due to ability to bond to Fe in place of O2, and comparably smelly, but even worse because of the likelihood of evolution of HCl through hydrolysis.

Nicodem - 3-4-2010 at 02:52

TCCA would certainly oxidize Na2S in a very exothermic reaction, however the product can not be trisodium cyanurate and SCl2 as these two must react between them. SCl2 and other electrophilic R-SCl species react with deprotonated imides (somewhat off topic, but the reaction is even synthetically useful and if you use S-chlorothiols you can obtain N-alkylthioimides, for a recent example see Synlett, 2009, 112-116). Furthermore according to a paper from the Russian Journal of Organic Chemistry (Zhurnal Organicheskoi Khimii, 22 (1986) 100-106) the haloimides react with elemental sulfur to give either N-halothio-imides or diimidosulfides. For example, NCS reacts with sulfur to give N-chlorothio-succinimide. Anyway, back to the topic, trisodium cyanurate is thermodynamicaly way uphill (just check the pKa3 of cyanuric acid!) and SCl2 is a relatively strong electrophile, so you would have a situation where the energy levels of the products are higher than of the starting materials. Instead, the most likely first step is the S-chlorination of Na2S giving sodium dichloroisocyanurate, NaCl and sulfur. Sulfur then reacts with TCCA giving an N-chlorothio-dichlorocyanuric acid which should get rapidly reduced by Na2S and so on until you get an intermediate unstable enough to fragment the cyanuric ring system. In short, your would likely end up with complete fragmentation to NaOCN, NaSCN, S, NaCl and who knows what. Sounds like an interesting experiment if you truly have anhydrous Na2S. Especially a finely powdered TCCA/Na2S or TCCA/S mixture should burst quite exothermically (unless they react already in the mortar which is very likely). However I would be more interested in the products of a controlled reaction of TCCA and S as this should give a more defined mixture of products in my opinion (among the volatile product possibly also S2Cl2 and SCl2).

BromicAcid - 3-4-2010 at 07:59

This jogged my memory on a fairly old post I remembered of Polverone's:
Quote:
In one of the most interesting long-term experiments, I mixed agricultural dusting sulfur with powdered trichloroisocyanuric acid. I initially added chloroform in hopes of achieving a slighlty more intimate union. The mixture was left in a narrow-necked bottle outside in the sun. The chloroform soon evaporated. Over a period of days I saw and smelled an interesting reaction. Clear yellow droplets of liquid accumulated on the glass, and a vaguely unhealthy odor came from the vessel. As the days went by, the droplets grew larger and moved further up the bottle. At the same time, the sulfur seemed to disappear entirely from the lower portion of the bottle. Solid sulfur and the liquid (S2Cl2?) both seemed to gradually creep upward under the influence of heat. By the time I took the bottle in for cleaning, I was unfortunately unable to recover any of the liquid. However, I shall try it again since it was relatively fast (compared to my other endeavors) and so interesting.

http://www.sciencemadness.org/talk/viewthread.php?tid=2275#p...

Not one to one of course since you are asking about the sulfide, and nothing conclusive since nothing was isolated. But still interesting none the less.

halogenstruck - 7-4-2010 at 10:39

2C3N3Cl3O3+6NaCl+3S==>6NaCNO+3SCl2 6apr2010
465g 351g 96g 309g
484.375 365.625 100 321.875 120% extra NaCl
0.5g 1g 0.1g 0.321875g
heating in a test tube after grinding NaCl/TCCA very well together and mixing with fine precipitated S powder==>heating bottom of test tube[dry]==>liquid makes the test tube wall wet[cold area] with yellow color and some crystal like deposited on test tube wall[S powder before reacting covered the test tube wall that when SCl2/S2Cl2 condensed on ,it possibly dissolved those S,then crystalized out]
smell of liquid is strong,pungent,somehow like sulfur and chlorine.
over dropping water droplets on the yellowish wet areas of the test tube,it release white fume of possibly HCl and decompose very fast with bubles[effervescence]
careful:Hazzard:[heating TCCA]maybe explosive decomposition due to NCl3 prescence although dilution by NaCl reduces the possible danger
result:for sure gives S2Cl2 at least if not SCl2.

halogenstruck - 7-4-2010 at 10:57

in present of a solvent,this mixture of NaCl/S/TCCA reacted much easier and faster.the same result

Taoiseach - 7-4-2010 at 21:58

Nice job!

What solvent did you use?

I wonder how to best separate the SCl2.

Formatik - 8-4-2010 at 14:40

Quote: Originally posted by halogenstruck  
careful:Hazzard:[heating TCCA]maybe explosive decomposition due to NCl3 prescence although dilution by NaCl reduces the possible danger


Yes, be cautious dry heating trichloroisocyanuric acid especially with oxidizables. Thermal degradation of it in inert gas is a known synthesis to carbonyl diisocyanate (colorless liquid which smells choking like SO2Cl2, probably extremely poisonous) alongside some NCl3, to a lesser extent Cl2 and CO2.

halogenstruck - 8-4-2010 at 16:22

actually i don`t have poly chlorinated solvents like tetrachloro ethylene chloroform tetrachlorocarbon now.
i used liquid paraffin.i know it`s not fit. it react with S to release H2S,...

entropy51 - 8-4-2010 at 17:40

Quote: Originally posted by halogenstruck  
result:for sure gives S2Cl2 at least if not SCl2.
For sure? Based on what? That it smelled funny? You probably made something, but you haven't a clue what is was, now do you?

Is this amateur science, or ignorant science? Which is to say, no science at all.

halogenstruck - 8-4-2010 at 19:09

read the text better.i chlorinatrd S before and smelled the same.if you don`t agree,just test it by yourself and write the results here:mad:
i tested it in very small amount and is not quantitative,just resulted in S2Cl2 or mixed S2Cl2/SCl2 OR S2Cl2/SxCl2 But not SCl2 because it`s yellow.resulted liquid was very little just to wet the wall.it immediately and violently reacted with water and released white HCl fume.i did not prepared that much to test its melting point or to make derivatives and i don`t have IR spectrometer.i am not certainly an amateur,i made at least 500 chemicals and sold them out although now i am out of that for some years and my equipments now are really primitive.

[Edited on 9-4-2010 by halogenstruck]

bbartlog - 5-12-2011 at 20:59

I performed the following experiment:

39g of TCCA was coarsely crushed and put into a 250ml RB flask. To this was added 79g of methanesulfonylmethane (MSM). A Hempel column was inserted atop the flask (mainly so that I could get a better view of any evolved vapors and possibly capture any unexpected foaming). Heat was applied with a bunsen burner until the MSM melted and the TCCA dissolved. A small amount (few mg) of white material was deposited on the lower end of the Hempel column, but overall there was no significant evolution of gas.
Heating was discontinued.
The Hempel colum was removed and 5g of sulfur added to the flask, along with a still head, thermometer, and receiver. The outlet from the receiving flask was stuffed with oven-dried cotton (to prevent entry of moisture) and a beaker of slightly warmed 5% ammonia was placed below the outlet to give visual indication of acidic fumes.
Heat was reapplied. The sulfur dissolved in the melt, which turned orange and began to bubble. Heating was discontinued, but an exothermic reaction appeared to take place as the materials foamed and rose into the still head before subsiding.
The still head and receiver were removed, cleaned, and dried in an oven (again) while the reaction flask was stoppered.
After reassembly of the apparatus, heating was continued again. A red-orange distillate began to pass over at 90C, continuing to pass over while gradually becoming lighter (nearly clear) until a temperature of 160C was reached in the still head. At this point I stopped heating the flask. A total of 17g of distillate was collected.

General observations:
- MSM looks inert enough to be used as a solvent in this reaction. I had worried that it might somehow be attacked/oxidized by TCCA, but there doesn't seem to be any sign of that.
- this reaction fumes. Don't do it in your kitchen or basement unless you have a fume hood. I did it in a barn with 30,000 cubic feet of air space and an open bay door (besides the ammonia as precaution) and it was still somewhat unpleasant.
- while there may well be substantial SCl2 and S2Cl2 in the distillate, the observed vapor temperature(s) - a smooth rise from 90C to 160C - don't give me a lot of optimism that the distillate is any sort of simple mixture.

Having managed to do this on a medium scale without catastrophe, I will probably try it on a somewhat larger scale (5x as large using a 2 liter flask) so that I have enough product to drive through my Hempel column while getting some decent stepwise temperature readings.

(update): on the following morning I see that the distillate has solidified to a glassy looking reddish material. That, obviously, is not S2Cl2 nor SCl2 (both have seriously subzero melting points).


[Edited on 6-12-2011 by bbartlog]