March 28, 2024, 09:59:00 AM
Forum Rules: Read This Before Posting


Topic: synthesis 6,6-Difluoro-bicyclo[3.1.0]hexane-3-carbaldehyde 494210-62-7  (Read 5440 times)

0 Members and 1 Guest are viewing this topic.

Offline wallysheng

  • Regular Member
  • ***
  • Posts: 10
  • Mole Snacks: +0/-0
Hi All,

Recently we started a new project with a need of 6,6-Difluoro-bicyclo[3.1.0]hexane-3-carbaldehyde (CAS494210-62-7). Has anybody done this compound before? Any opinion on this case? We appreciate if someone can provide relative info or paper. Thanks!    :)

Wally

Offline sjb

  • Global Moderator
  • Sr. Member
  • ***
  • Posts: 3653
  • Mole Snacks: +222/-42
  • Gender: Male
Cis or trans?

Assuming I've converted name to structure correctly, how about RCM on diallyl malonate, then Krapcho monodecarboxylation, addition of difluorocarbene to the double bond, then reduction of the acid to the aldehyde?

Offline wallysheng

  • Regular Member
  • ***
  • Posts: 10
  • Mole Snacks: +0/-0
It seems ok but if so we need to start this case from scratch. We appreciate your opinion. Thank you very much!

Offline sjb

  • Global Moderator
  • Sr. Member
  • ***
  • Posts: 3653
  • Mole Snacks: +222/-42
  • Gender: Male
I'm not saying that's the *only* way to make it - what are your thoughts?

Offline wallysheng

  • Regular Member
  • ***
  • Posts: 10
  • Mole Snacks: +0/-0
Thanks!
But we'd like to know a relative mature route for this synthesis. Using the starting material you mentioned above we don't know how to monitor the reaction. It hard to monitor the progress of the reaction. Have you done familar case before?

Offline sjb

  • Global Moderator
  • Sr. Member
  • ***
  • Posts: 3653
  • Mole Snacks: +222/-42
  • Gender: Male
Well, the first step I mentioned above has decent precedent, in e.g. http://dx.doi.org/10.1021/jo030005p  (3  :rarrow: 4), and is used as a model reaction for the activity of RCM in general, from what I can see. For the decarboxylation, perhaps http://dx.doi.org/10.1016/S0040-4039(00)90519-7 is the original report. Reduction has too many references to list. Carbene addition - perhaps http://dx.doi.org/10.1039/b212232d ?

As to monitoring, I appreciate that the reactants don't really have chromophores, but depending on your set-up, I guess staining TLCs, or NMR or ... ?

What were you planning on using as a starting material and your route?

Offline kiwi

  • Chemist
  • Full Member
  • *
  • Posts: 229
  • Mole Snacks: +20/-0
  • Gender: Male
If cost is an issue, both sodium trifluoroacetate and sodium chlorodifluoroacetate are cheaper sources of :CF2, as they both fragment on heating:

X-CF2-CO2Na -> :CF2 + NaX + CO2

I imagine you're going to need to use modern chemistry techniques (TLC or HPLC, NMR etc) to monitor the reaction no matter which route you choose. 


Offline sjb

  • Global Moderator
  • Sr. Member
  • ***
  • Posts: 3653
  • Mole Snacks: +222/-42
  • Gender: Male
If cost is an issue, both sodium trifluoroacetate and sodium chlorodifluoroacetate are cheaper sources of :CF2, as they both fragment on heating:

X-CF2-CO2Na -> :CF2 + NaX + CO2

True, I'm sure there are easier / cheaper methods out there, I was just going on a quick use of a FWSE, as I'm very limited in what literature I can easily access.

Offline wallysheng

  • Regular Member
  • ***
  • Posts: 10
  • Mole Snacks: +0/-0
We have not fixed the route yet? We are discussing and considering your methods. Thanks!!!

Sponsored Links