June 20, 2019, 07:28:00 AM
Forum Rules: Read This Before Posting


Topic: Nuciferine+CHCl3/NaOH  (Read 3797 times)

0 Members and 1 Guest are viewing this topic.

Offline Rutherford

  • Sr. Member
  • *****
  • Posts: 1868
  • Mole Snacks: +59/-29
  • Gender: Male
Nuciferine+CHCl3/NaOH
« on: February 25, 2014, 10:57:57 AM »
What is the product of the attached reaction? I think that maybe the formyl group is introduced in one of the aromatic rings but I am not sure.

Offline discodermolide

  • Chemist
  • Sr. Member
  • *
  • Posts: 5038
  • Mole Snacks: +404/-70
  • Gender: Male
    • My research history
Re: Nuciferine+CHCl3/NaOH
« Reply #1 on: February 25, 2014, 11:02:59 AM »
Chloroform plus conc. NaOH generates dichlorocarbene.
So look up the chemistry of carbenes. Also look up what you can do with the products. Start with simple examples such as addition to double bonds or insertion into C-H bonds or any other X-H bond. The product is effectively a "What" after hydrolysis?
Development Chemists do it on Scale, Research Chemists just do it!
My Research History

Offline Rutherford

  • Sr. Member
  • *****
  • Posts: 1868
  • Mole Snacks: +59/-29
  • Gender: Male
Re: Nuciferine+CHCl3/NaOH
« Reply #2 on: February 25, 2014, 11:22:28 AM »
Cyclopropanation would destroy the aromaticity, so I exclude it. The only reactions that wouldn't disturb the ring system would be insertion between N and Me or O and Me. As one product is obtained I would go with N-Me, but is it true?

Offline discodermolide

  • Chemist
  • Sr. Member
  • *
  • Posts: 5038
  • Mole Snacks: +404/-70
  • Gender: Male
    • My research history
Development Chemists do it on Scale, Research Chemists just do it!
My Research History

Offline Rutherford

  • Sr. Member
  • *****
  • Posts: 1868
  • Mole Snacks: +59/-29
  • Gender: Male
Re: Nuciferine+CHCl3/NaOH
« Reply #4 on: February 25, 2014, 12:01:57 PM »
Okay, would this be the mechanism?

Offline discodermolide

  • Chemist
  • Sr. Member
  • *
  • Posts: 5038
  • Mole Snacks: +404/-70
  • Gender: Male
    • My research history
Re: Nuciferine+CHCl3/NaOH
« Reply #5 on: February 25, 2014, 12:03:20 PM »
That looks ok. Great ;D
Development Chemists do it on Scale, Research Chemists just do it!
My Research History

Offline Rutherford

  • Sr. Member
  • *****
  • Posts: 1868
  • Mole Snacks: +59/-29
  • Gender: Male
Re: Nuciferine+CHCl3/NaOH
« Reply #6 on: February 25, 2014, 12:15:20 PM »
Good. Thank you again.

Offline CrimpJiggler

  • Full Member
  • ****
  • Posts: 113
  • Mole Snacks: +5/-3
Re: Nuciferine+CHCl3/NaOH
« Reply #7 on: March 02, 2014, 02:30:22 AM »
Cyclopropanation would destroy the aromaticity, so I exclude it. The only reactions that wouldn't disturb the ring system would be insertion between N and Me or O and Me. As one product is obtained I would go with N-Me, but is it true?

Nuciferine isn't fully aromatic though, the aliphatic portion about the N atom would be susceptible to cyclopropanation. My memory of carbene reactions is hazy, but from what I remember its not just double bonds they can react with, they can also insert themselves between C-H bonds. I agree with you that the carbene won't touch the benzene rings (won't disrupt the pi stacking anyway). As I said my knowledge is a bit hazy, I can't remember what the regiochemistry from carbene insertions.

Offline opsomath

  • Chemist
  • Full Member
  • *
  • Posts: 469
  • Mole Snacks: +50/-8
Re: Nuciferine+CHCl3/NaOH
« Reply #8 on: March 03, 2014, 10:12:39 AM »
I am pretty sure those are normal formylation conditions and that it'll react ortho to the top methoxy from your figure to make a CHCl2 group which hydrolyses to the formyl group.

Offline discodermolide

  • Chemist
  • Sr. Member
  • *
  • Posts: 5038
  • Mole Snacks: +404/-70
  • Gender: Male
    • My research history
Re: Nuciferine+CHCl3/NaOH
« Reply #9 on: March 03, 2014, 10:44:41 AM »
The book chapter I provided the link to suggests that this is a carbene reacting with the N lone pair.
50% NaOH and chloroform are conditions used for generating dichlorocarbene.
Now if the carbene does anything else, well it would not surprise me. But no yields are provided so it is difficult to say what else may be going on here.
Certain is that the CHCl2 will give a formyl on hydrolysis.
Development Chemists do it on Scale, Research Chemists just do it!
My Research History

Sponsored Links