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Alexander doesn't need to be 36. That's about the other country that you're marrying with. Your issue is that they have already married someone else, so they can't do that for 5 more years.
So my recommendation is to marry Alexander as soon as possible - on his birthday, ideally. Because the pool of candidates is rather small (only other Orthodox countries, which basically means Moldova, Serbia, and Wallachia), so you basically need to be quicker than the others.
Anyway, this popularity increase seems to be damn near a requirement to get Alexander in charge, because on my end, even if I leave him as the only character in the Gentry Assembly, at 0 popularity it just generates new characters. What I find works best is to get Alexander the +25 popularity from the marriage, and then leave at least one Gentry Assembly guy, preferably the one with -10 popularity. This way the game is less likely to generate new guys.