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Q: Organic Mechanism ( No Answer,   5 Comments )
Question  
Subject: Organic Mechanism
Category: Science > Chemistry
Asked by: shal04-ga
List Price: $15.00
Posted: 12 May 2004 20:49 PDT
Expires: 11 Jun 2004 20:49 PDT
Question ID: 345546
I am having trouble with a mechanism that I am working on.  The
mechanism can be found here:
http://www.uwrf.edu/~shalyn.r.morrow/chem
Heat is added for the reaction to proceed.
Answer  
There is no answer at this time.

Comments  
Subject: Re: Organic Mechanism
From: stuyshick-ga on 13 May 2004 16:38 PDT
 
Dear Shal,
Great question! Probably the most exciting 7 minutes of my day.

Since the reaction occurs with heat alone, it seems very likely to be
a Woodward-Hoffman rearrangement with 4n+2 pi electrons. Its too bad
that I can't paste images here but I did post the mechanism on my
school website. Check it out at: http://homepages.nyu.edu/~ms1864/

It is a concerted step reaction and the numbers in blue are only
written as a suggested order but everything really happens in one
step. It makes perfect sense because if you count the arrows, there
are 5 of them. It is a 10 pi electron system (4n+2 where n=2) which,
by woodward-hoffman rules, should go with heat (not light). Glad to
help. Let me know what you think.

P.S. Sorry for the crappy artwork but its the best I could get out of Paint.
Subject: Re: Organic Mechanism
From: acrh2-ga on 13 May 2004 18:08 PDT
 
Where exactly did you find 10 pi electrons?
Subject: Re: Organic Mechanism
From: shal04-ga on 13 May 2004 21:58 PDT
 
I am assuming that it was meant that there are 6 pi electrons, which
still follows the 4n+2 rule, instead of 10.
Subject: Re: Organic Mechanism
From: dr_bob-ga on 13 May 2004 23:05 PDT
 
sorry stuyshick, but i disagree that this is a concerted mechanism,
you just don't have the orbital overlap for this to happen in a single
step.

Try first, a 3,3 sigmatropic shift, followed by another.
Subject: Re: Organic Mechanism
From: shal04-ga on 13 May 2004 23:39 PDT
 
Thank you to both of you for your help!  It is greatly appreciated.  I
was originally thinking a 3,3 shift, but could not get it to work.  I
think that I now have it first doing a 3,3 shift leaving the oxygen
chain alone, and then after that another 3,3 shift involving the
oxygen chain this time.  Thanks again!!!

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