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Author: Subject: Someone experience with Cycloalkenes to cyclocarbonyls
MrMario
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[*] posted on 22-2-2016 at 03:00
Someone experience with Cycloalkenes to cyclocarbonyls


I read that cyclohexene/cyclopentene can be converted with N2O to produce cyclohexanon and cyclopentanon and would like to know more about this procedure. If anyone has experience, please let me know.
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CharlieA
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[*] posted on 22-2-2016 at 06:14


Where is your reference, please?
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MrMario
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[*] posted on 22-2-2016 at 06:31


http://link.springer.com/article/10.1023%2FA%3A1016564818065...

U need to click on "Look inside" to see the preview of the paper.
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UC235
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[*] posted on 22-2-2016 at 07:17


The reaction conditions for this are 250C, 100atm in an autoclave.
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CharlieA
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[*] posted on 22-2-2016 at 12:19


Thanks for the link. I don't think that the 250*C is a problem, but 100 atm? How do you propose to develop (and contain) that much pressure? You are a much braver man than I, Mario. If you try this, please let us know how it turns out-Ciao, Charlie
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DraconicAcid
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[*] posted on 22-2-2016 at 12:43


100 atm of N2O? That's a laugh and a half.

I'm sure it would be much easier to add water across the double bond with dilute sulphuric acid, and then oxidize the alcohol with bleach.

[Edited on 22-2-2016 by DraconicAcid]




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clearly_not_atara
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[*] posted on 22-2-2016 at 21:00


If you just feel like running a vapor-phase reaction, singlet oxygen (which is dangerous) gives 3-hydroperoxycyclopentene. This can be converted into cyclopentenone in a variety of ways, or directly to more interesting compounds.

Otherwise I believe the traditional answer involves mercury acetate and potassium dichromate.

[Edited on 23-2-2016 by clearly_not_atara]

[Edited on 23-2-2016 by clearly_not_atara]
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UC235
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[*] posted on 22-2-2016 at 22:20


Quote: Originally posted by clearly_not_atara  
If you just feel like running a vapor-phase reaction, singlet oxygen (which is dangerous) gives 3-hydroperoxycyclopentene. This can be converted into cyclopentenone in a variety of ways, or directly to more interesting compounds.


Actually, this can be done in the liquid phase (perhaps diluted in methanol) in oxygen atmosphere using methylene blue or rose bengal as a sensitizer and a fairly powerful light source. Reduction to the allylic alcohol is trivial involving aq. Na2SO3 or zinc and acetic acid
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DJF90
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[*] posted on 23-2-2016 at 01:58


Quote: Originally posted by UC235  

Actually, this can be done in the liquid phase (perhaps diluted in methanol) in oxygen atmosphere using methylene blue or rose bengal as a sensitizer and a fairly powerful light source.


See here for further elaboration: http://curlyarrow.blogspot.co.uk/2007/04/fun-with-singlet-ox...
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MrMario
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[*] posted on 23-2-2016 at 05:14


Sooo, i guess it's not something what could be done as a hobby chemist.. Don't think I have the equipment to reach ~100 bar.
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Dr.Bob
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[*] posted on 23-2-2016 at 10:44


Reaching 100 bar is not a problem at all. Containing it in one place is, however. I bet Bert can elaborate on the first step.
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CuReUS
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[*] posted on 24-2-2016 at 03:29


Quote: Originally posted by UC235  
The reaction conditions for this are 250C, 100atm in an autoclave.

Its a russian paper,what do you expect ? :D

Mario,if you want to do something exotic to get the ketone from the alkene,You could try the Wacker oxidation ,which gives very high yields (97 % for cyclohexene)
http://www.sciencemadness.org/talk/viewthread.php?tid=10007#...
but It will to cost you ;)

[Edited on 24-2-2016 by CuReUS]
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