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Chemistry Forums for Students => Organic Chemistry Forum => Topic started by: orgobot on May 06, 2008, 07:39:42 PM

Title: cycloheptene into cyclohexanone?
Post by: orgobot on May 06, 2008, 07:39:42 PM
Hi everyone,
I'm working on a synthesis problem that really looks like a Mannich reaction (ketone, formaldehyde, amine).  The thing is we need to start with given molecules as our only carbon source.  I'm given cycloheptene as a starting molecule but if it is a Mannich reaction, it looks like I need a cyclohexanone.

My question is, is it possible to synthesize cyclohexanone from cycloheptene?  My first thought was ozonolysis --> aldol but then I'm stuck.  I've also tried to figure out other ways that aren't Mannich reactions but I get stuck there.  Does anyone have any hints in the right direction?  Thanks  :) 

edit: my bad. I meant cyclohexanone, not cyclohexanal... :-X
Title: Re: cycloheptene into cyclohexanal?
Post by: macman104 on May 06, 2008, 09:19:32 PM
If you provide the structure, people would be able to say whether they agree with your choice of Mannich.

What about addition with an aqueous halogen, oxidation of the alcohol to a ketone and then favorskii rearrangement to get the carboxylic acid.  If you need the aldehyde, reduce to the alcohol and oxidize with PCC.
Title: Re: cycloheptene into cyclohexanone?
Post by: orgobot on May 06, 2008, 11:50:46 PM
Apologies! First, I meant cyclohexanone, since Mannich needs a ketone.
I'm not sure how to properly name the structure, but it looks like the result of a Mannich given a cyclohexanone, formaldehyde, and a methyl amine.
Title: Re: cycloheptene into cyclohexanone?
Post by: macman104 on May 07, 2008, 01:11:47 AM
So...like this?
Title: Re: cycloheptene into cyclohexanone?
Post by: orgobot on May 07, 2008, 01:14:32 AM
yes, that is it.
Title: Re: cycloheptene into cyclohexanone?
Post by: Yarr on May 07, 2008, 06:04:01 AM
Quote from: Orgobot
My question is, is it possible to synthesize cyclohexanone from cycloheptene?

1) Treatment with CrO2Cl2 in acetone to get 2-chlorocycloheptanone.

2) 2-chlorocycloheptanone + NaHO, then acidify, to get cyclohexanecarboxilic acid.

3) Br2, HgO, heat, to get cyclohexyl bromide.

4) Oxidation with DMSO to get cyclohexanone.
Title: Re: cycloheptene into cyclohexanone?
Post by: orgobot on May 07, 2008, 09:47:34 AM
Hi Yarr, thanks for the response.  I don't think I've ever heard of CrOCl2, and we're only allowed to use reagents we know, though...  Does anyone have other suggestions?  Until then I'm going to keep working at it :)
Title: Re: cycloheptene into cyclohexanone?
Post by: macman104 on May 07, 2008, 04:50:31 PM
Hi Yarr, thanks for the response.  I don't think I've ever heard of CrOCl2, and we're only allowed to use reagents we know, though...  Does anyone have other suggestions?  Until then I'm going to keep working at it :)
Surely if you are learning the mannich reaction you're able to use other reactants.  If not, all the CrO2Cl2 does is what the first 2 steps of my synthesis does:  chlorine water, then oxidation of the alcohol to a ketone.  Which is where you are at for step 2 of Yarr's synthesis.
Title: Re: cycloheptene into cyclohexanone?
Post by: Rico on May 14, 2008, 10:42:41 AM
Hello

I'm not quite sure what it is you're discussing here but one thing I got out of it was that you needed to synthesise cyclohexanone from cycloheptene and I have a suggestion on how to do that (see jpeg attached). Ozonolysis of cycloheptene and workup with hydrogenperoxide to the diacid. Esterification and treatment with base giving via a claisen (dieckmann) condensation a beta-keto ester, that after hydrolysis can be decarboxylated to give cyclohexanone.

Rico