| Pages:
1
2 |
Rhodanide
Hazard to Others
Posts: 348
Registered: 23-7-2015
Location: Ｔｈｅ ８０ｓ
Member Is Offline
Mood: That retro aesthetic
|
|
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
|
|
|
Chemvironment
Harmless
Posts: 23
Registered: 1-10-2017
Member Is Offline
Mood: No Mood
|
|
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.
|
|
|
DraconicAcid
International Hazard
Posts: 4356
Registered: 1-2-2013
Location: The tiniest college campus ever....
Member Is Offline
Mood: Semi-victorious.
|
|
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.
|
|
|
Rhodanide
Hazard to Others
Posts: 348
Registered: 23-7-2015
Location: Ｔｈｅ ８０ｓ
Member Is Offline
Mood: That retro aesthetic
|
|
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.
|
|
|
Sigmatropic
Hazard to Others
Posts: 307
Registered: 29-1-2017
Member Is Offline
Mood: No Mood
|
|
Among other things It can be used to make acetyl chloride and hence acetic anhydride.
|
|
|
clearly_not_atara
International Hazard
Posts: 2799
Registered: 3-11-2013
Member Is Offline
Mood: Big
|
|
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 562 times
|
|
|
Melgar
Anti-Spam Agent
Posts: 2004
Registered: 23-2-2010
Location: Connecticut
Member Is Offline
Mood: Estrified
|
|
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!
|
|
|
Rhodanide
Hazard to Others
Posts: 348
Registered: 23-7-2015
Location: Ｔｈｅ ８０ｓ
Member Is Offline
Mood: That retro aesthetic
|
|
These are great and all, but all the complicated organic chem experiments are out of my reach...
|
|
|
Chemvironment
Harmless
Posts: 23
Registered: 1-10-2017
Member Is Offline
Mood: No Mood
|
|
Its a polar aprotic solvent like dmf, acetone, or dmso. Just use it as such.
|
|
|
Rhodanide
Hazard to Others
Posts: 348
Registered: 23-7-2015
Location: Ｔｈｅ ８０ｓ
Member Is Offline
Mood: That retro aesthetic
|
|
Ok, great.
|
|
|
Nicodem
Super Moderator
Posts: 4230
Registered: 28-12-2004
Member Is Offline
Mood: No Mood
|
|
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!
|
|
|
woelen
Super Administrator
Posts: 8027
Registered: 20-8-2005
Location: Netherlands
Member Is Offline
Mood: interested
|
|
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.
|
|
|
Rhodanide
Hazard to Others
Posts: 348
Registered: 23-7-2015
Location: Ｔｈｅ ８０ｓ
Member Is Offline
Mood: That retro aesthetic
|
|
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?
|
|
|
BromicAcid
International Hazard
Posts: 3253
Registered: 13-7-2003
Location: Wisconsin
Member Is Offline
Mood: Rock n' Roll
|
|
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]
|
|
|
Perchlorate
Harmless
Posts: 3
Registered: 18-11-2017
Member Is Offline
Mood: Strongly Oxidising, with the possibility of fire
|
|
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
|
|
|
DraconicAcid
International Hazard
Posts: 4356
Registered: 1-2-2013
Location: The tiniest college campus ever....
Member Is Offline
Mood: Semi-victorious.
|
|
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.
|
|
|
Rhodanide
Hazard to Others
Posts: 348
Registered: 23-7-2015
Location: Ｔｈｅ ８０ｓ
Member Is Offline
Mood: That retro aesthetic
|
|
| 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
|
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!
|
|
|
zed
International Hazard
Posts: 2284
Registered: 6-9-2008
Location: Great State of Jefferson, City of Portland
Member Is Offline
Mood: Semi-repentant Sith Lord
|
|
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.
|
|
|
Rhodanide
Hazard to Others
Posts: 348
Registered: 23-7-2015
Location: Ｔｈｅ ８０ｓ
Member Is Offline
Mood: That retro aesthetic
|
|
| 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.
|
|
|
Metacelsus
International Hazard
Posts: 2539
Registered: 26-12-2012
Location: Boston, MA
Member Is Offline
Mood: Double, double, toil and trouble
|
|
| Quote: Originally posted by zed | Or Acetonitrile + H2O > Ethanol + HCN. Depending on where you are, on the "Bell Curve", problems could arise.
|
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]
|
|
|
clearly_not_atara
International Hazard
Posts: 2799
Registered: 3-11-2013
Member Is Offline
Mood: Big
|
|
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.
|
|
|
JJay
International Hazard
Posts: 3440
Registered: 15-10-2015
Member Is Offline
|
|
That's interesting... Grignards are more stable when exposed to air than organozinc reagents... does the Blaise reaction require an inert atmosphere?
|
|
|
DraconicAcid
International Hazard
Posts: 4356
Registered: 1-2-2013
Location: The tiniest college campus ever....
Member Is Offline
Mood: Semi-victorious.
|
|
| 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.
|
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.
|
|
|
clearly_not_atara
International Hazard
Posts: 2799
Registered: 3-11-2013
Member Is Offline
Mood: Big
|
|
| 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]
|
|
|
JJay
International Hazard
Posts: 3440
Registered: 15-10-2015
Member Is Offline
|
|
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]
|
|
|
| Pages:
1
2 |
![[*]](images/xpblue/default_icon.gif){kind=icon}
