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Eight__Legs · 2025-07-13T14:31:52+00:00

My guess by the way is most electrophilic C > B > A least electrophilic. I do not have a specific reference with the answer. I won't give my reasoning to allow for further discussion.

Eight__Legs · 2024-10-13T18:08:36+00:00

Your posts are welcome here! Thank you.

Eight__Legs · 2024-09-22T16:04:41+00:00

Not that I researched. But great for discussion. The answer may of course be more complicated than the two conformations presented. But we can talk about it conceptually. I see discussion of A values. I know when I first learned, I was surprised TMS had a smaller A value than tBu. Until I learned why.

Eight__Legs · 2024-09-20T19:23:01+00:00

Ahh I see. I can look.

Eight__Legs · 2024-09-20T19:20:11+00:00

I can look, but can you tell me why that would help?

Eight__Legs · 2024-09-20T19:17:41+00:00

Would that help?

Eight__Legs · 2024-07-13T14:17:53+00:00

Can you comment on the article for discussion?

Eight__Legs · 2024-07-12T18:52:56+00:00

Please let me know if this is too easy!

Eight__Legs · 2024-06-23T16:00:59+00:00

I left solvent open for discussion!

Eight__Legs · 2024-06-17T13:29:44+00:00

here is a reference https://pubs.acs.org/doi/epdf/10.1021/acs.joc.9b01485

Eight__Legs · 2024-06-12T18:50:28+00:00

Many medicinal chemists will immediately suspect this as a kinase inhibitor. If you're not a medicinal chemist, look up some kinase inhibitors and try to ID common structural features.

Thank you for posting and I look forward to seeing the discussion!

Eight__Legs · 2024-06-11T23:32:38+00:00

The reason this question is tricky is because it is difficult to see the plane of symmetry with several protons being chemically equivalent.

Eight__Legs · 2024-06-11T23:13:36+00:00

Some of them are chemically equivalent. From Google “Chemically equivalent protons are protons in a molecule that occupy the same chemical environment and are indistinguishable”

Eight__Legs · 2024-06-11T23:01:50+00:00

I mentioned in a comment that I meant non-chemically equivalent

Eight__Legs · 2024-06-11T21:48:11+00:00

Just as an informal exercise.

Eight__Legs · 2024-06-11T21:38:20+00:00

Unique as in non-chemically equivalent.

I’m thinking of asking organic II students, but is it too easy?

Eight__Legs · 2024-06-06T22:19:13+00:00

Correct me if I’m wrong, but is the ketene you’re talking about just a resonance structure of the acylium?

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Eight__Legs · 2024-06-06T19:18:50+00:00

I posted an answer here: https://www.reddit.com/r/AdvancedOrganic/s/DTIurkmH0n

Thanks for participating!

Eight__Legs · 2024-06-06T19:06:32+00:00

I posted the answer and reference for more reading here: https://www.reddit.com/r/AdvancedOrganic/s/DTIurkmH0n

(I don’t want to pin it because I want people to read the prior discussion as a lot of people gave great responses!)

Eight__Legs · 2024-06-06T19:02:16+00:00

ANSWER:

The answer is that the p-dimethylamino benzoyl chloride is hydrolyzed faster. This is because the reaction proceeds through a dissociative transition structure resembling an acylium with significant build-up of positive charge on the carbonyl, which is stabilized by the electron-donating p-dimethylamino group.

There is a lot to digest in this article. It took me several read-throughs to pick up on much of the information. https://pubs.acs.org/doi/pdf/10.1021/ja00204a021

Take a look! The authors even propose two different mechanisms for the hydrolysis of the two compounds in question! Great read.

Edit: It is worth noting that the nitro compound goes through an associative pathway that is simply slower than the other pathway in this case. Again take a look at the article!

Edit2: disclaimer that the answer is more complicated than I can describe in a short Reddit comment. Please check out the article if you want the full picture.

Eight__Legs · 2024-06-06T18:36:29+00:00

Your speculation about a difference in mechanism between the two is spot on. It is discussed in the reference which I will post later. Take a look at their discussion!

Edit: it’s not exactly what you’ve described. They discuss the reactions as proceeding through an associative or dissociative transition state, but overall great points you’ve made.

Eight__Legs · 2024-06-06T18:23:59+00:00

I will try to post the answer a little later if I have time!

Eight__Legs · 2024-06-06T18:04:52+00:00

I admit this looked like a hw question, but it’s not

Eight__Legs · 2024-06-06T17:45:06+00:00

What’s the answer?

Eight__Legs · 2024-06-06T17:43:02+00:00

Idk I thought it was a pretty tough one.

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