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Rhodanide
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Acetonitrile uses
Hi everyone. I have a good amount of Acetonitrile (500mL), and don't really know what to do with it. Are there any interesting reactions which I can
do with it, or complexes which can be made? I know it burns with a pinkish flame, but I don't really want to waste it that way. Thoughts or
suggestions? I couldn't really find much online about this.
Thanks,
-R/T
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Chemvironment
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If I recall correctly some college buddies were using it for DNA synthesis or peptide sequences or something of that nature. Idk if that floats your
boat.
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DraconicAcid
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I seem to recall that it coordinated to copper(I) quite well, and that copper(I) is the stable form of copper in acetonitrile solution.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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Rhodanide
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Quote: Originally posted by Chemvironment  | | If I recall correctly some college buddies were using it for DNA synthesis or peptide sequences or something of that nature. Idk if that floats your
boat. |
That's.. interesting, but it sounds more like biochemistry as opposed to inorganic, simple organic and organometallic chemistry, which is my interest
area.
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Sigmatropic
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Among other things It can be used to make acetyl chloride and hence acetic anhydride.
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clearly_not_atara
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It is a good solvent for the preparation of organozinc reagents from allyl, benzyl, and aryl halides (usually bromides), the latter using a cobalt (I)
catalyst generated in situ. See e.g.:
Allyl and benzyl halides:
https://www.thieme-connect.com/products/ejournals/html/10.10...
https://www.thevespiary.org/rhodium/Rhodium/Vespiary/talk/fi...
http://www.journal.csj.jp/doi/pdf/10.1246/cl.1981.1135 (slightly inferior to glyme in this case, 73% vs 83% yield)
Aryl halides:
http://onlinelibrary.wiley.com/doi/10.1002/chem.200204604/fu...
https://s3.amazonaws.com/academia.edu.documents/44508014/Che...
http://www.sciencedirect.com/science/article/pii/S0040403903...
http://www.sciencedirect.com/science/article/pii/S0040403905...
The arylzinc reagents can be transmetallated to arylcopper reagents as long as the arene is not electron-deficient, in which case a biaryl formation
is observed; Le Gall et al 2005, attached. Presumptive dimerization mechanism: Ar-CuX + Ar'-ZnX >> ZnX2 + Cu + Ar-Ar'
[Edited on 8-12-2017 by clearly_not_atara]
Attachment: legall2005.pdf (99kB)
This file has been downloaded 560 times
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Melgar
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It can be reacted with Grignard reagents to produce methyl ketones on hydrolysis.
The first step in the process of learning something is admitting that you don't know it already.
I'm givin' the spam shields max power at full warp, but they just dinna have the power! We're gonna have to evacuate to new forum software!
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Rhodanide
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These are great and all, but all the complicated organic chem experiments are out of my reach...
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Chemvironment
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Its a polar aprotic solvent like dmf, acetone, or dmso. Just use it as such.
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Rhodanide
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Ok, great.
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Nicodem
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Old topic, already discussed:
https://www.sciencemadness.org/whisper/viewthread.php?tid=13...
It helps using the forum search engine before opening new topics.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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woelen
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It can be used as a solvent for making strongly fluorescent ruthenium complexes. I did some experiments with Ru-bipyridine complexes, dissolved in
CH3CN. With addition of some Mg-filings and dilute HCl you get amazing very bright orange fluorescence.
So, if you have ruthenium and bipyridine, then acetonitrile is a very interesting solvent.
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Rhodanide
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I saw that thread already, but it didn't answer my questions. The thread was mostly filled with people pondering how to dry Acetonitrile, and maybe
one or two threads which actually discussed uses. I did see your post about the Epoxidation of Alkenes, which interests me. I have a brand new bottle
of 35% H2O2, so maybe I'll give that a try. I just need to find an Alkene lying around... (suggestions?) Can it Epoxidize
organics like soybean oil?
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BromicAcid
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Quite a rare find indeed 
I procured acetonitrile sometime back to make trimethylsilyl nitrate from trimethylsilyl chloride and silver nitrate dissolved in acetonitrile, the
silver chloride crashes out. It was a literature prep that went exactly as planned.
[Edited on 12/14/2017 by BromicAcid]
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Perchlorate
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I managed to find a 4L bottle of HPLC-grade Acetonitrile (For the equivalent of 27 US dollars), so I have a similar problem now... 
Some uses include Chemplayer's Acetyl Chloride: https://www.youtube.com/watch?v=Q2ArDw0vf2Q
Production of [Cu(CH3CN)4]+ : sorry, couln't find a good preparation...
Of course, Acetonitrile can be used as a solvent for a bunch of reactions, but the most interesting for me are probably:
Fluorination of Pyridines and Diazines with AgF2 in Acetonitrile :http://www.orgsyn.org/Content/pdfs/procedures/v94p0046.pdf
Preparation of Sulfonyl Chlorides via N-Chlorosuccinimide in Acetonitrile; http://www.orgsyn.org/Content/pdfs/procedures/v91p0116.pdf
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DraconicAcid
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Dissolve any anhydrous copper(II) salt in acetonitrile, and stir over clean copper wire or shavings.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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Rhodanide
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| Quote: Originally posted by Perchlorate | I managed to find a 4L bottle of HPLC-grade Acetonitrile (For the equivalent of 27 US dollars), so I have a similar problem now...
Some uses include Chemplayer's Acetyl Chloride: https://www.youtube.com/watch?v=Q2ArDw0vf2Q
Production of [Cu(CH3CN)4]+ : sorry, couln't find a good preparation...
Of course, Acetonitrile can be used as a solvent for a bunch of reactions, but the most interesting for me are probably:
Fluorination of Pyridines and Diazines with AgF2 in Acetonitrile :http://www.orgsyn.org/Content/pdfs/procedures/v94p0046.pdf
Preparation of Sulfonyl Chlorides via N-Chlorosuccinimide in Acetonitrile; http://www.orgsyn.org/Content/pdfs/procedures/v91p0116.pdf
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Dear god man, now you've got enough VOCs to knock out a herd of elephants! If I'm correct, HPLC is the purest you can get, right? What an incredible
find, 4L for $27. Now just go win the lottery!
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zed
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Keep in mind, there are occasionally toxicity problems with Acetonitrile. Historically, it was used industrially in "sealed" systems. When it
entered the realm of more common chemical lab usage, some deaths were precipitated.
Handle with caution. Treat with respect.
Seems like hydrolysis could take place in several ways. Acetonitrile+ H2O > Acetic Acid + Ammonia Or Acetonitrile + H2O > Ethanol + HCN.
Depending on where you are, on the "Bell Curve", problems could arise.
Folks sometimes slosh the stuff around, get it all over themselves, then go home, go to sleep...... and never wake up again. Seems like Nail Salons,
lost a few beauticians that way.
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Rhodanide
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| Quote: Originally posted by zed | Keep in mind, there are occasionally toxicity problems with Acetonitrile. Historically, it was used industrially in "sealed" systems. When it
entered the realm of more common chemical lab usage, some deaths were precipitated.
Handle with caution. Treat with respect.
Seems like hydrolysis could take place in several ways. Acetonitrile+ H2O > Acetic Acid + Ammonia Or Acetonitrile + H2O > Ethanol + HCN.
Depending on where you are, on the "Bell Curve", problems could arise.
Folks sometimes slosh the stuff around, get it all over themselves, then go home, go to sleep...... and never wake up again. Seems like Nail Salons,
lost a few beauticians that way.
|
I just think it's fascinating how most nitriles are around 30-90mg/kg for the LD50, while Acetonitrile is somewhere in the range of over 2,400mg/kg.
It's still toxic though, and still a Nitrile, so there's that hazard.
If it's around as toxic as Toluene or similar solvents, then I should have nothing to worry about.
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Metacelsus
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| Quote: Originally posted by zed | Or Acetonitrile + H2O > Ethanol + HCN. Depending on where you are, on the "Bell Curve", problems could arise.
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It would be methanol + HCN, since acetonitrile is CH3CN.
Also, for that organozinc reaction mentioned by clearly_not_atara, I'm surprised the organozinc reagent doesn't react with the acetonitrile to form an
imine (which would be the analogous reaction for a Grignard organomagnesium). Maybe it's just that the aldehyde (or imine formed in situ by reaction
of the aldehyde and an amine) reacts more quickly and consumes all the organozinc before it has a chance to react with the acetonitrile.
[Edited on 12-19-2017 by Metacelsus]
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clearly_not_atara
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There is a reaction between organozinc reagents and nitriles but it requires a reflux:
http://www.organic-chemistry.org/namedreactions/blaise-react...
Aldehyde addition occurs at rt or lower. Imines and acyl halides/anhydrides also work. Weinreb amides and thioesters have not been tried IIRC. Ketones
are apparently unreactive because someone would definitely have tried. Isocyanates might also react... if you're for some reason disappointed that the
rxn isn't dangerous enough.
I really don't see why the rxn is above anyone's head, it's much easier than a Grignard from all the reports I've read.
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JJay
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That's interesting... Grignards are more stable when exposed to air than organozinc reagents... does the Blaise reaction require an inert atmosphere?
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DraconicAcid
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| Quote: Originally posted by zed | | Seems like hydrolysis could take place in several ways. Acetonitrile+ H2O > Acetic Acid + Ammonia Or Acetonitrile + H2O > (m)Ethanol + HCN.
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Wait, are you suggesting an Sn2 reaction in which cyanide is the leaving group? I glare at you skeptically, because cyanide is a crappy leaving
group, and the triple-bonded carbon is much more susceptible to attack than the methyl one.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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clearly_not_atara
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| Quote: Originally posted by JJay | | That's interesting... Grignards are more stable when exposed to air than organozinc reagents... |
Where did
you hear this? Some organozincs are air-stable period:
http://onlinelibrary.wiley.com/doi/10.1002/chem.201403015/fu...
Are you comparing dialkylzincs to alkylmagnesium halides? The reactions I referred to use organozinc halides which are less reactive.
Dialkylmagnesiums are from what I've heard even more reactive than dialkylzincs. Most procedures with organozinc call for an inert atmosphere but so
do most Grignards.
[Edited on 19-12-2017 by clearly_not_atara]
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JJay
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I had always thought it would be a good idea to use an inert atmosphere with Grignards, and I was actually comparing dialkylzincs (which is what most
people mean when they refer to organozinc compounds) to alkylmagnesium halides and saw that a dialkyl zinc wasn't exactly being formed here or at
least not isolated; that was why I asked the question. The paper you cited uses a protecting group to make organozinc compounds air stable, has
nothing to do with acetonitrile, and doesn't answer the question.
[Edited on 19-12-2017 by JJay]
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