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Chemistry Forums for Students => Organic Chemistry Forum => Topic started by: AlphaScent on July 24, 2014, 02:01:23 PM

Title: Ring closure of Citral
Post by: AlphaScent on July 24, 2014, 02:01:23 PM

So I am trying to figure out the best way to synthesize Isopiperitenone.  The enone analog of the product attached.
I think allylic oxidation of d-limonene will give poor yields and mixtures of products.  Mostly carvone.

Though direct allylic oxidation may end up being my only option, I can across a reference from a paper about the synthesis of isopiperitenol from citral.  I cannot get access to this reference.  It states that you can make isopiperitenol from citral in one step.  I am trying to think about what that one step could be since I cannot find the journal. 

I am not asking for anyone to give me copyrighted material.  Please do not send me it if you find the reference.

Verley A. Bull. Soc. Chim. Fr. 1899; 21; 408

I think the mechanism could be acid catalyzed?? The acid attached to the oxygen. Giving a negative charge on the carbonyl carbon that can attack the tetrasubstituted double bond...I think I am wrong

Any help is greatly appreciated

Title: Re: Ring closure of Citral
Post by: discodermolide on July 24, 2014, 02:37:24 PM

Could this be an intra-molecular Prins reaction?

Title: Re: Ring closure of Citral
Post by: AlphaScent on July 24, 2014, 07:14:57 PM

I was wrong.  Meant a POSITIVE charge on the carbonyl carbon.  After a quick google search it seems to me that it is indeed an allyic alcohol product Prins reaction.

It seems to me that you mad also get the diol, but you would be able to separate those two quite easily.

Have to do some literature research on this reaction.

Thanks Disco!!!

Title: Re: Ring closure of Citral
Post by: cerambyx on February 13, 2025, 08:16:55 AM

Hi,

did you eventually make any progress on isopiperitenol?

Title: Re: Ring closure of Citral
Post by: cerambyx on February 13, 2025, 08:18:13 AM

Also if you still need the paper, I have it. If you would need it and wrote to me about it, I definitely wouldn't share it with you. ;)

Title: Re: Ring closure of Citral
Post by: billnotgatez on February 13, 2025, 05:32:01 PM

@cerambyx
The last time op member was on this site was
November 01, 2024, 02:19:06 PM
and the original post was
July 24, 2014, 02:01:23 PM

they might be back
they might remember the post

Title: Re: Ring closure of Citral
Post by: cerambyx on February 14, 2025, 09:02:52 AM

I assumed the op would get notified about the reply.

If not, then.. It's a shame idk

Title: Re: Ring closure of Citral
Post by: Borek on February 14, 2025, 11:22:50 AM

Quote from: cerambyx on February 14, 2025, 09:02:52 AM

I assumed the op would get notified about the reply.

Notifications are not automatic and need to be enabled by the user.

No idea if AlphaScent did.