May 29, 2024, 05:57:57 AM
Forum Rules: Read This Before Posting


Topic: unexpected NMR results for a morpholine-based amide  (Read 5289 times)

0 Members and 1 Guest are viewing this topic.

Offline Babcock_Hall

  • Chemist
  • Sr. Member
  • *
  • Posts: 5630
  • Mole Snacks: +324/-24
unexpected NMR results for a morpholine-based amide
« on: March 01, 2023, 10:08:48 AM »
https://organicchemistrydata.org/hansreich/resources/nmr/?index=nmr_index%2F13C_shift#cdata84

Good Morning,

We made (EtO)2P(O)CH2C(O)N(-CH2CH2OCH2CH2-), where the amide is the morpholine group.  As expected, four of the carbon atoms showed coupling to phosphorus.  There are two signals, 47.3 ppm and 42.4 ppm, that I believe to be -NCH2- groups.  Given that there is restricted rotation around the amide (-NC(O)-) bond, seeing two peaks is understandable (see link for a couple of examples).  However, the peak that I assigned to -OCH2- at 66.7 ppm is the only signal in this region other than the CH3CH2[/sub]O- peak, which is one of the doublets.  I am a little puzzled why restricted rotation would affect one carbon atom and not the other.

Later I may post a little bit about the H-1 spectrum as well.

Offline rolnor

  • Chemist
  • Sr. Member
  • *
  • Posts: 2228
  • Mole Snacks: +149/-10
Re: unexpected NMR results for a morpholine-based amide
« Reply #1 on: March 05, 2023, 05:57:45 AM »
To see the effect off restricted rotation the atom needs to get two different environments magneticaly, mayby one off the atoms does not have this?

Offline Babcock_Hall

  • Chemist
  • Sr. Member
  • *
  • Posts: 5630
  • Mole Snacks: +324/-24
Re: unexpected NMR results for a morpholine-based amide
« Reply #2 on: March 05, 2023, 07:07:32 PM »
A colleague of mine suggested something similar, which is that the difference in the two environments of the CH2O groups may be small enough to put these two nuclei into the fast-exchange regime.  I need to refresh my memory on chemical exchange to make sure that I understood correctly.

Offline rolnor

  • Chemist
  • Sr. Member
  • *
  • Posts: 2228
  • Mole Snacks: +149/-10
Re: unexpected NMR results for a morpholine-based amide
« Reply #3 on: March 09, 2023, 05:06:53 AM »
Its at least possible, can you maybe cool the probe? Or look at proton-nuclei?

Offline Babcock_Hall

  • Chemist
  • Sr. Member
  • *
  • Posts: 5630
  • Mole Snacks: +324/-24
Re: unexpected NMR results for a morpholine-based amide
« Reply #4 on: March 09, 2023, 10:18:41 AM »
I just looked at the H-1 NMR.  The 8 hydrogen atoms of the morpholine group form a multiplet centered near 3.68 ppm.  It looks like a triplet in which each of the three signals is further split into two or three signals.

When I went to Hans Reich's site, I found a few examples of amides in which the two carbon atoms directly attached to the nitrogen atom had C-13 chemical shift differences around 2-3 ppm.  I have not searched extensively for morpholine-containing compounds specifically.
« Last Edit: March 09, 2023, 10:53:25 AM by Babcock_Hall »

Offline rolnor

  • Chemist
  • Sr. Member
  • *
  • Posts: 2228
  • Mole Snacks: +149/-10
Re: unexpected NMR results for a morpholine-based amide
« Reply #5 on: March 11, 2023, 12:47:44 AM »
Great! You have plain DMF with large differences in shift...

Offline Babcock_Hall

  • Chemist
  • Sr. Member
  • *
  • Posts: 5630
  • Mole Snacks: +324/-24
Re: unexpected NMR results for a morpholine-based amide
« Reply #6 on: March 14, 2023, 12:30:40 PM »
I am sorry, but I do not follow you.  Do you mean that DMF is a model compound?  One of the models at Hans Reich's site is N,N-dibenzyl-2(triphenylsilyl)acetamide.  The benzylic -CH2- groups are found at 48.2 and 50.7 ppm.
« Last Edit: March 14, 2023, 12:51:11 PM by Babcock_Hall »

Offline rolnor

  • Chemist
  • Sr. Member
  • *
  • Posts: 2228
  • Mole Snacks: +149/-10
Re: unexpected NMR results for a morpholine-based amide
« Reply #7 on: March 14, 2023, 08:52:56 PM »
Yes, I mean that the compound you have can be more prone to restricted rotation than DMF because its a larger molecule. Maybe its not a very important observation. You have been working on these compounds for some time now, how are you doing, do you see any more bio-activity? Do you have any progress?

Offline Babcock_Hall

  • Chemist
  • Sr. Member
  • *
  • Posts: 5630
  • Mole Snacks: +324/-24
Re: unexpected NMR results for a morpholine-based amide
« Reply #8 on: March 15, 2023, 09:32:12 AM »
I have seen some astonishing results in whole cell assays.  I need to raise my game synthetically.

Offline rolnor

  • Chemist
  • Sr. Member
  • *
  • Posts: 2228
  • Mole Snacks: +149/-10
Re: unexpected NMR results for a morpholine-based amide
« Reply #9 on: March 16, 2023, 06:11:08 PM »
Great! Please let me now if I can help you. That explaines why you continue the work then.

Offline wildfyr

  • Global Moderator
  • Sr. Member
  • ***
  • Posts: 1773
  • Mole Snacks: +203/-10
Re: unexpected NMR results for a morpholine-based amide
« Reply #10 on: March 16, 2023, 10:25:21 PM »
At this point you should consider giving Rolnor the lowest priority authorship if you write a paper :)

Offline rolnor

  • Chemist
  • Sr. Member
  • *
  • Posts: 2228
  • Mole Snacks: +149/-10
Re: unexpected NMR results for a morpholine-based amide
« Reply #11 on: March 18, 2023, 05:16:24 AM »
Aaaahhh, that was nice wilfyr, I give you a molsnack!

Sponsored Links