Thursday 10/1/2018¶
Morning realisation¶
I made an assumption about the cyclisation of 3 4, in that I assumed that the newly formed ring would re-aromatise, but this step should really only re-aromatise the left hand ring, so the chemistry will look more like this:
I’m pretty sure this changes the applications again, though I’ll do some reading to see what I can come up with
Post supervisor meeting¶
I dare say that most of what I thought about this project so far was wrong, but now I have some direction which is useful:
- Get the outline done for submission on Sunday evening.
- Do a risk assessment on all the chemistry involved, particularly 2\(\ce{->}\)3, as I’ve been informed it can be quite dangerous if not performed correctly.
- perform synthesis 2 3 (under strict supervisor guidance) whilst concurrently performing 0\(\ce{->}\)1\(\ce{->}\)2, since it’s well understood chemistry.
- Thoroughly characterise 3 to verify that we have the correct product.
- look into appropriate dienophiles for 3\(\ce{->}\)4, as it needs to be an ‘inverse demand’ Diels Alder reaction, with substituents on the dienophile acting as electron donating groups (EDGs), since we have EWGs on the 3
- In conjunction with step 5, I can explore other types of chemistry, such as nucleophilic addition top see if the nucleophile will attack the diene, the carbonyl carbon of the imide, or the aromatic rings
- Time permitting, look into ceric ammonium nitrate (CAN) as an oxidising agent to re-aromatise 4 back into a naphthalene core.
The applications for all of this, beyond the curious “exploring what chemistry is possible” are all the primary application of NDIs1, as well as to open up a new direction of chemistry for NDI research
It was also suggested that I should go all the way from synthesising the initial NDI (1) from naphthalene dianhydride (NDA)2 (0) as well as starting with the stock 2, for the sake of completeness.
-
Ohno, M.; Koide, N.; Sato, H.; Eguchi, S. Synthesis of Heterocycle-Linked [60] Fullerene Derivatives by Heterocyclic o-Quinodimethane Diels-Alder Reaction and Self-Sensitized Photooxygenation of the Cycloadducts. Tetrahedron 1997, 53 (27), 9075–9086. https://doi.org/10.1016/S0040-4020(97)00600-5. ↩
-
Suraru, S. L.; Würthner, F. Strategies for the Synthesis of Functional Naphthalene Diimides. Angew. Chemie - Int. Ed. 2014, 53 (29), 7428–7448. https://doi.org/10.1002/anie.201309746. ↩