garage chemist
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Mercaptans from CS2, alcohol + alkali
I once read that someone prepared butyl mercaptan from 1-butanol (I have 50ml left from my old chemistry set) and carbon disulphide in a basic
envoronment.
Would this work? What would the reaction proceed like- maybe the CS2 forms some weird thiocarbonate salt with the base? How would that thiocarbonate
look like (structure), and how would it react with the butanol?
I have no CS2, but if it turns out to be a really useful reagent, I'll try to make some.
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sparkgap
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garage chemist,
As far as I am aware of (and looking at references besides), there is no note of carbon disulfide in basic medium reacting with alcohols; however, it
is known that alkyldithiocarbamates are produced when basic CS<sub>2</sub> is reacted with the appropriate amine (with ammonia, the
formation equilibrates with decomposition unless an appropriate electrophile is introduced.)
But the absence from the literature (except from where you have read it; can you recall?) does not, of course, exclude that such a reaction may
happen. I would also suppose that a dithiocarbonate intermediate (R-O-C(=S)-S<sup>-</sup> may be involved; as to rearrangement into the alkylsulfide (since the medium is basic, the mercaptan will be afforded
upon quenching with acid), I am not certain.
sparky (^_^)
P.S. I hope you are acutely aware of carbon disulfide's properties before attempting to make it. 
"What's UTFSE? I keep hearing about it, but I can't be arsed to search for the answer..."
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Esplosivo
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Regarding carbon disulfide, I find it is not an abnormally toxic chemical. It can be compared to aromatics such as phenylamine and benzene with
respect to its toxic effect, which when handled safely are quite harmless. I am more worried about the 'may cause reproductive disorders'
part than anything else  . But I guess it requires some damn excessive inhalation
of the stuff for this to occur, or else contact with the liquid itself, both of which can be prevented with proper ventilation and equipment. What do
you think?
Btw sparkgap, thank you for your help on the P thread.
Theory guides, experiment decides.
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guaguanco
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CS2 is also as flammable a material as you'd EVER want to deal with.
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neutrino
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No kidding, hot water will make this stuff catch fire. I find I suddenly want to make some now...
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garage chemist
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White Phosphorus self- ignites at 50°C. I once had some molten phosphorus under warm water in a test tube and poured all the stuff into a beaker
filled with water and, what do you think, the shit violently catches fire and some of the burning phosphorus stayed at the surface of the water to
crackle and spit burning phosphorus everywhere. WP is the most flammable material I am aware of. Nothing comes close.
I remembered where I found the mercaptan synthesis from CS2: on the powerlabs message board.
[Edited on 14-4-2005 by garage chemist]
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sparkgap
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Well, for sure I wasn't hinting at inflammability when I was talking about "properties", since we handle combustible stuff quite often.
Esplosivo, you seem to think on the same wavelength as I. 
sparky (^_^)
"What's UTFSE? I keep hearing about it, but I can't be arsed to search for the answer..."
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mick
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CS2 and base might give you a dithiocarbonate and an alcohol could react
mick
CS2 smells of rotten cabbage. can be ignited at around140oC (ether can be ignite at around 180 oC). It is a cold blue flame and it has been linked to
genetic damage in males and other stuff.
mick
[Edited on 15-4-2005 by mick]
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neutrino
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Its autoignition point is lower--somewhere around 90*C.
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unionised
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"As far as I am aware of (and looking at references besides), there is no note of carbon disulfide in basic medium reacting with alcohols"
Sparkgap, you might not be aware of it, but the xanthate rayon process relied on it.
[Edited on 16-4-2005 by unionised]
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sparkgap
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How could I have forgotten?!?  The vivid orange of the xanthogenate (or xanthate,
as it is sometimes called) was the most stunning part of a trip to a textile factory I had taken quite a while back... (except for those dyeing vats;
nice colors )
Thanks for the reminder, unionised.
sparky (^_^)
P.S. Has anyone attempted CS<sub>2</sub> yet?
"What's UTFSE? I keep hearing about it, but I can't be arsed to search for the answer..."
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Esplosivo
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If I remember correctly BromicAcid has successfully prepared a sample of the stuff. I tried to last summer but my heat source was not good enough, my
container did not seal as tightly as it should have and ended up with a complete, burning, mess.
[Edited on 17-4-2005 by Esplosivo]
Theory guides, experiment decides.
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