Wednesday 30/1/2018¶
Oxidation of 1 to form 2 (AS04)¶
For completeness, I would still like to synthesise and purify 1, even though we have a stock sample. As with everything, the synthesis is not the problem, the problem is that I’m not particularly confident with running columns yet, as I haven’t been taught the technique particularly thoroughly yet.
fig:AS04NMR, In fractions 1 and 2 there is a fair amount of precursor product (1), but across all three fractions we can’t see the dione, which would have a 2 proton peak at \(\sim\)8.25 ppm. What we can see though is a fair amount of “H grease” and degraded products. I’m not entirely sure what the UV degraded 2 would look like to be able to predict what it’s NMR might look like.Purification of side experiment - dry synthesis of 1 from 0¶
1 (fig:drycrystalline). NMR spectra were taken of the samples in \(\ce{CDCl3}\).The spectra showed that samples A and B were pure 1 and as such they have been combined and are currently drying to be able to determine the yield. While sample B showed a small proportion of 1, it introduced some new peaks that may present some answers to what the pink stuff is (fig:dryspectra).
Oxidation of 1 to form 2 (AS06)¶
To a 50 mL round bottom flask was added 51 mg of 1, 150.6 mg of \(\ce{NaIO4}\) and 20 mL of DCM/ACN/\(\ce{H2O}\) (9:1:1). With constant stirring, 14.6 mg of \(\ce{RuCl3}\) was added and the flask was refluxed at 40\(^\circ\)C overnight.
Reduction of 2 to form 3 (AS05)¶
Finally getting on to real crux of the research project. We have sodium metal, in the THF still, with \(\ce{N2}\) bubbling through the system and the THF is finally dry. We’re finally ready to mode on to the synthesis of 3.
As per 1 To a round bottom flask was added 79.8 mg of 2 and \(\sim\)70 mg of \(\ce{NaBH4}\). To this was added \(\sim\)30 mL of dry THF, straight from the solvent still. The flask was flushed with \(\ce{N2}\) gas and was topped with a balloon full of \(\ce{N2}\) to ensure an inert and dry atmosphere. The reaction was left at room temperature with stirring overnight.
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Maniam, S.; Sandanayake, S.; Izgorodina, E. I.; Langford, S. J. Unusual Products from Oxidation of Naphthalene Diimides. Asian J. Org. Chem. 2016, 5 (4), 490–493. https://doi.org/10.1002/ajoc.201600048. ↩