Chemical Forums
1 Hour
1 Day
1 Week
1 Month
Forever
December 01, 2024, 02:42:14 PM
Forum Rules
: Read This Before Posting
Home
Help
Search
Login
Register
Chemical Forums
Chemistry Forums for Students
Organic Chemistry Forum
Organic Chemistry Forum for Graduate Students and Professionals
failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction
« previous
next »
Print
Pages: [
1
]
Go Down
Topic: failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction (Read 4406 times)
0 Members and 1 Guest are viewing this topic.
Babcock_Hall
Chemist
Sr. Member
Posts: 5709
Mole Snacks: +330/-24
failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction
«
on:
January 25, 2023, 07:22:59 PM »
We have used Masamune-Roush conditions in Horner Wadsworth Emmons reactions with good results on a number of occasions. Last week we had a rare failure using 5-nitrofuraldehyde and diethyl methylsulfonylmethylphosphonate, with DBU as the base. So far the only product that I have identified by NMR is the phosphonate starting material. There may be some aldehyde remaining. TLC with UV detection showed many spots, some of which faded with time.
Does this furan have a propensity to react in other ways? I am told it may do single electron chemistry, but I don't have a reference for this. If we substituted the corresponding thiophene for this furan, are we likely to do any better? Thanks for any ideas.
«
Last Edit: January 25, 2023, 07:36:07 PM by Babcock_Hall
»
Logged
Babcock_Hall
Chemist
Sr. Member
Posts: 5709
Mole Snacks: +330/-24
Re: failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction
«
Reply #1 on:
January 26, 2023, 10:17:45 AM »
One more modest point of interest. The darkness of the color waxed and waned over the fractions. Yet, the first two pools that we analyzed by H-1 NMR were nearly pure diethyl methylsulfonylmethylphosphonate, the colorless starting material.
Logged
Babcock_Hall
Chemist
Sr. Member
Posts: 5709
Mole Snacks: +330/-24
Re: failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction
«
Reply #2 on:
January 26, 2023, 10:19:32 PM »
Furan is weakly aromatic, and thiophene is strongly aromatic. That may tip the balance in favor of a Horner reaction with respect to thiophene.
Logged
Babcock_Hall
Chemist
Sr. Member
Posts: 5709
Mole Snacks: +330/-24
Re: failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction
«
Reply #3 on:
February 09, 2023, 11:48:15 AM »
The corresponding thiophene-based aldehyde gave a more typical reaction and was purified with little difficulty. Although there was at least one other product, it moved much more slowly through the silica column, and we have not attempted to isolate it.
Logged
Babcock_Hall
Chemist
Sr. Member
Posts: 5709
Mole Snacks: +330/-24
Re: failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction
«
Reply #4 on:
September 30, 2024, 09:06:46 AM »
Would the corresponding reaction with formylnitropyrrole behave more like the furan (which failed) or the thiophene (which succeeded), or do we just have to try it and see? The pyrrole is intermediate in aromaticity between the furan and the thiophene, so I don't know.
Would replacing the nitro group with a carboxylate ester change the reaction for either a furan or a pyrrole. My sense is that the carboxylate group is less electron-withdrawing, but I don't have a feel for how much.
Logged
rolnor
Chemist
Sr. Member
Posts: 2299
Mole Snacks: +154/-10
Re: failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction
«
Reply #5 on:
October 01, 2024, 03:36:13 AM »
I think pyroll is much more aromatic in character than furan, so yes, I think it will be similar to thiophene. Yes, carboxylate is less EW than nitro, hard to say how much. As you suggest, just try, there is good hope.
Logged
Print
Pages: [
1
]
Go Up
« previous
next »
Sponsored Links
Chemical Forums
Chemistry Forums for Students
Organic Chemistry Forum
Organic Chemistry Forum for Graduate Students and Professionals
failure of 2-nitrofuraldehyde in Horner Wadsworth Emmons reaction