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Author: Subject: Tertbutylthiol synthesis
Hexacoralli
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[*] posted on 15-1-2025 at 02:25
Tertbutylthiol synthesis


Hello, I am new to science madness and that's my first post! I ve read some about making thiols with gringard reagent way but there is horribly little information about it. I ve figured out synthesizing tertbutyl mercaptane from reaction of corresponding gringard reagent with elemental sulfur in diethyl ether. Something simmilar was described on Wikipedia, but without exact details. Then I am going to extract the thiol with water solution of NaOH. And maybe add to it some acid and extract free thiol with some Organic solvent. And my question is, is it kinda possibile to work and what conditions should i keep the reaction (temperature etc) Have you done sth simmilar already?
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Fery
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[*] posted on 15-1-2025 at 05:52


You could also consider this way:
https://www.chem.ucalgary.ca/courses/353/Carey5th/Ch15/ch15-...
tert butanol + HCl or HBr -> tert butyl chloride or bromide
tert butyl bromide + thiourea -> tert butyl isothiouronium bromide
tert butyl isothiouronium bromide + NaOH -> tert butyl thiol
(add some reducing agent maybe Na2S2O3 in the last step to prevent oxidation into dithiol)
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Dr.Bob
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[*] posted on 15-1-2025 at 05:56


Just to make sure you understand, that is the chemical that is added to natural gas in ppm to make it smell. If you make this, you almost certainly will have every neighbor for blocks calling in a gas leak. We used it in grad school, and it was always causing issues, even in a chemistry building, with hoods, and with thiol trapping equipment... I would aim at higher MW thiols to start or maybe just make isonitriles, they stink also, but not like a gas leak.
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Hexacoralli
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[*] posted on 16-1-2025 at 00:26


But if I keep it in its deprotonated form, will it cause any stinking problem? Then I could safely acidify the sample in some uninhabitaed area. I am considering gringard reagent way becsuse don't have thiourea and just want to try this reaction.

[Edited on 16-1-2025 by Hexacoralli]
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bnull
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[*] posted on 16-1-2025 at 19:07


Welcome to the forum!

I recommend you read the Mad Science FAQ and the other FAQ. They pretty much cover what can and cannot be done here.

The Library is quite interesting. Two books from there that I recommend are Brauer's Handbook of Preparative Inorganic Chemistry and Vogel's A Textbook of Practical Organic Chemistry. Both are somewhat old (1960s or so), the availability may have changed for some if not most of the reagents; still, they are valuable for the standard procedures and references they contain.

Bretherick's Handbook of Reactive Chemical Hazards and Leonid Lerner's Small-Scale Synthesis of Laboratory Reagents would be good complements to any other books you may have.

***

Quote: Originally posted by Hexacoralli  
I ve figured out synthesizing tertbutyl mercaptane from reaction of corresponding gringard reagent with elemental sulfur in diethyl ether. Something simmilar was described on Wikipedia, but without exact details.

Check out reference [3] from the Wikipedia article (Rheinboldt et al., "Tertiäres Butylmercaptan", https://doi.org/10.1002/prac.19321340901, in German). According to this paper, you need absolutely dry sulfur (recrystallised from carbon disulfide and dried over P2O5 and activated charcoal) and a dry inert atmosphere (they suggest hydrogen, something I don't recommend at all for an amateur). They also suggest an excess of Grignard reagent over sulfur, 0.8 mol of sulfur for each 1 mol of t-butylmagnesium chloride, to avoid the formation of disulfides and other undesirable products.

Chapter 4 (Preparation of Thiols) of The Thiol Group, part 1, volume 1, deals with the preparation of thiols, including addition of sulfur to organometallics.

The paper by Rheinboldt mentions another paper on the matter by H. Wuyts, "Sur le mécanisme de l'action du soufre et du sélénium sur les organomagnésiens". It begins on page 405 of the Bulletin de la Societé Chimique de France, series 4, volume 5 (1909) (here, in French). I can't access it now because of cache issues (I probably messed up some configuration).

Finally, there's this book: Organic Chemistry of Bivalent Sulfur.

Do you have any use for it or is it just for curiosity's sake?

Given that its odor threshold is less than 0.33 ppb (yep, that low), I'd try another substance.

[Edited on 17-1-2025 by bnull]




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Hexacoralli
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[*] posted on 19-1-2025 at 13:27


I was just looking for an interesting and smelly compound to synthesize and wanted to utilize somehow my tert buthyl chloride
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