Ormarion
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Thietane synthesis, a goofy looking compound
Hello you all, i wanted to share today a synthesis i performed some days ago
As some might know i like experimenting with organosulfur compound
Looking into the synthesis of tetrahydrothiophene starting from dihalogeno butane, and Na2S in DMF i figured that i could try using some of my 1,3
dibromo propane in order to make the 4 atom ring version of it.
The whole procedure was inspired by the following Orgsyn article (https://www.orgsyn.org/demo.aspx?prep=CV4P0892)
To start, in a erlenmeyer flask i added 80ml of DMF with a magnetic stirrer and heated the whole thing until reaching a slight reflux
On the side a 60% solution of 10g of Na2S was prepared in hot water, and on the other side 25g of 1,3 dibromopropane (sourced from TCI) was sampled
Both reagents were added slowly by a septum using a seringe during a few minutes, controlling the ebullition of the mix
At this time the reaction mix became slightly cloudy, and a slight sulfurous smell was detectable
The reaction was refluxed for the next 2 hours.
At this point my whole lab was definitely smelling like a mix of burnt meat and city gas
The apparatus was arranged to distill away the product, after 2h of distillation i obtained around 1g of thietane as a yellow liquid, denser than
water with a extremely strong sulfurous smell.
In order to increase the yeild i added 5 more grams of Na2S in water to the reaction mix and continued to distill (upon addition the mix turned into a
dark emerald green color for some reason)
After pushing the distillation further i then added water to the cloudy mixture and extracted it with DCM (i would avoid using NaOH or NaCl if you use
DCM as it can mess up the emulsion)
DCM was then slowly evaporated leaving me with 2,7g of a yellow liquid with a boiling point of 94°C, still having a very strong sulfur smell.
I could in theory check the refractory index but i dont really want to make my whole refractometer smell like shit, and so far the product seem to
behave like expected
Litterature obtained a yeild of 70% for tetrahydrothiophene, in my case the final yeild was of 30%. I believe that using chloro bromo propane instead
of dibromo might prevent polymerisation of some kind and favor the cyclisation, but the straining in such small rings might also be a reason for the
low yeild.
I have no real uses for it but is a funny looking compound that i tought was nice to share about
Here you can see some pictures of the compound in question
Thanks for reading :3
 
[Edited on 24-11-2023 by Ormarion]
[Edited on 24-11-2023 by Ormarion]
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UC235
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Do you have any actual evidence that you made the compound in question? I would think that with such significant ring strain, just about any other
reaction product would be likely. Fortunately you used an excess of Na2S because there's likely a real risk of a bis-haloalkylthioether forming which
is a sulfur mustard analogue.
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Tsjerk
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Boiling point of 94 degrees? You could question how this was measured, but this sounds quite definitive.
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Ormarion
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Thanks for the messages, i haven't performed any precise analysis on it (i could eventually do a NMR) but i found some procedures using this pathway
online. Above that the boiling point measured was by trying to boil the liquid itself when finishing to evaporate dcm as well as during distillation.
Concerning the mustart problem this was something i tought about wich is why i took extreme care during the handling of it, but even you people know
that with organo thiols, even the smallest amount can stink a entire lab
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EF2000
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Thietane and its derivatives are alarm pheromones of mice (ref 1ref 2). If you have a problem with rodents, you can now scare them off
Wroom wroom
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