December 22, 2024, 10:54:08 PM
Forum Rules: Read This Before Posting


Topic: Surprisingly few methylation protocols?  (Read 5007 times)

0 Members and 1 Guest are viewing this topic.

Offline mir

  • Fascinated organic chemist
  • Chemist
  • Full Member
  • *
  • Posts: 310
  • Mole Snacks: +13/-3
  • Gender: Male
  • Visit my blog: mir.humle.be
    • My humble homepage with norwegian articles
Surprisingly few methylation protocols?
« on: September 10, 2006, 07:15:32 AM »
I am trying to add a methyl group to an arene. But I find only three synthesis-protocolls:

Wurtz-fittig:    from bromoarene derivate with CH3I and Na
Friedel-Craft:   directly on the ring with CH3Cl and FeCl3/AlCl3
Methylation by Birch-reduction:  MTM-Cl and ZnCl followed by raney-nickel

Other hits on scifinder involved photolysis reactions.

Did I miss anything?  :o

Thank you for all suggestions...
No single thing abides, but all things flow.
Fragment to fragment clings, and thus they grow
Until we know and name them.
Then by degrees they change and are no more
The things we know.
- Titus Lucretius Carus

http://www.ife.no

Offline HP

  • Chemist
  • Full Member
  • *
  • Posts: 350
  • Mole Snacks: +33/-5
  • Gender: Male
Re: Surprisingly few methylation protocols?
« Reply #1 on: September 10, 2006, 08:38:13 AM »
For methylation arenes also possible Grignard reaction of MeMgI with Ar-X or Ar-MgX + Me-I--> Ar-Me. I am thinking also for this possible path:
From arendiazonium salt with MeLi
[Ar-N=N+]Cl- + CH3-Li -->LiCl + Ar-N=N-CH3 heat-->N2 + Ar. +CH3. -->Ar-Me  ???
Though Ar-X + MeLi possible reaction too :)
xpp

Offline movies

  • Organic Minion
  • Retired Staff
  • Sr. Member
  • *
  • Posts: 1973
  • Mole Snacks: +222/-21
  • Gender: Male
  • Better living through chemistry!
Re: Surprisingly few methylation protocols?
« Reply #2 on: September 11, 2006, 12:15:33 PM »
Other options are formylation and reduction or nucleophilic addition to an aryne.

Can't think of any others off the top of my head.  Any reason you can't start from the arene with the Me already installed?

Offline mir

  • Fascinated organic chemist
  • Chemist
  • Full Member
  • *
  • Posts: 310
  • Mole Snacks: +13/-3
  • Gender: Male
  • Visit my blog: mir.humle.be
    • My humble homepage with norwegian articles
Re: Surprisingly few methylation protocols?
« Reply #3 on: September 12, 2006, 04:51:22 AM »
Any reason you can't start from the arene with the Me already installed?

I may have to start with a group of substrates. Of course, I can order a better starting point in my synthesis. But what is the challenge in that?  ;D

No single thing abides, but all things flow.
Fragment to fragment clings, and thus they grow
Until we know and name them.
Then by degrees they change and are no more
The things we know.
- Titus Lucretius Carus

http://www.ife.no

Sponsored Links