Hey. I have experience making both 3,4,5-Trimethoxynitrostyrene (TMNS) and 2,5-Dimexthoxynitrostyrene (DMNS). Won't read over this whole thread but will paste my thoughts from a post I made on another forum as regards to the choice of catalyst:
2-HEAA (2-(hydroxy)ethylammonium acetate) from ethanolamine and glacial acetic acid does seem to work better on 3,4,5-Trimethoxybenzaldehyde than ethylenediamine (as ethylenediamine diacetate) does. Recently I ran two experiments on 150g 3,4,5-TMBA.
For the first batch of 150g I used 1.6 mol. eq. of nitromethane to the TMBA and a 1.5 mol. eq. of ethanolamine to the TMBA.
First I poured the NM onto the TMBA, and continued pouring glacial acetic acid until the TMBA dissolved. As for the GAA amount I believe I poured 161 mL or 2.81 mol. of GAA + then I used (1.5x 0.765 mol) of GAA to make the 2-HEAA in a separate container. So it was a total of 3.96 mol. eq. of GAA I used it seems. Hmm... Might be that 4 mol. eq. of GAA is a good amount to use.
Used a 1:1 ethanolamine to GAA mol. eq. to make the 2-HEAA. Poured at once the ethanolamine onto the GAA. The mixture heated up suddenly to 120 °C, fumes are released. Mixed for a bit and covered the separate beaker, cooled the mixture to slightly above room temp. Anyway, made sure the TMBA + NM + GAA was fully dissolved, and dumped in the thick, syrupy 2-HEAA at once. Immediate colour change, I heat to 35 °C and let it spin. Turns slightly darker, yellow close to orange. Sometime between the 1h 30 min and 2 hr mark the whole beaker became a thick mass. Everything precipitated out, but I was away and did not witness the sight. The colour is very pretty. A perfect yellow.
But I could not dry anything and weigh anything as my pump broke.
Later I recrystallized in a guesstimate of 8 mL/g MeOH. Could be that you could use even less MeOH. Somewhere on this forum it might be written 0.2 g/ mL 3,4,5-TMNS to methanol. But here is where I screwed everything up. As usual with the re-x I screw up. For some strange reason I decide to do a hot filtration, bunch lost on the filter paper. Then I poured a bunch down the drain. Poured out the mother liquor. So yield was poor, but still had a decent amount of some very pretty looking 3,4,5-TMNS.
With the second batch of 150g I once again went with a 1.6 mol. eq. of nitromethane, but now used less ethanolamine, a 1.3 mol. eq. to the TMBA. I also prepared the 2-HEAA separately. Mixing GAA and ethanolamine stuff really heats up, so I take the heat away from the NM and TMBA. This time I also used a total of 5 mol. eq. of GAA (a portion poured onto 3,4,5-TMBA + NM, and a portion used to make the 2-HEAA). Now I spun for a longer time with more heat, first at 45 °C, then I dropped to 35 °C. Nothing precipitated out like last time. When I stopped mixing and removed from heat, as the mixture cooled, then did crystals begin to appear. I sucked almost dry with a mostly working pump, then I recrystallized with 8 mL/g IPA. I could have used even less IPA, as it heats up everything should dissolve. Maybe even with 7 mL/g IPA.
Why not just use IPA instead of MeOH?
But this time the batch was a bit darker yellow and yields were poor.
Next time when preparing 3,4,5-TMNS I would use a 1.8 - 2 mol. eq. of ethanolamine, 1.8 - 2 mol. eq. nitromethane, 4 mol. eq. of GAA or the amount to dissolve TMBA.
And also in conclusion ethanolamine (used as 2-HEAA) for 3,4,5-TMNS does seem to be a better pick than ethylenediamine (used as ethylenediamine diacetate) makes for a cleaner product. But also could be other variables like heat I used before.
2,5-DMNS seems to be very easy and forgiving to prepare, also super cool watching the orange hairs appear. 3,4,5-TMNS less forgiving but also not that difficult, just use 2-HEAA.
Maybe others are interested but this 2-HEAA also gives 95%+ yields in the production of P2NP, it really is great stuff.
