You know I've never even considered the idea of the mechanics of the extraction, but I see psilocin is very soluble in ethanol and barely soluble in water, so it is a base extraction, using alcohol and clearly would be a poor choice of an extraction solvent (for the base) then there's psilocybin the phosphate Ester, it is soluble in water, barely soluble in ethanol and stable and forms crystals according to several reliable accounts.
I suppose the fumerate or other acid salt would be water soluble and form crystals also, which would be a "straight to acid " extraction. Makes you think. Clearly after you did 2 pulls with ethanol you would want to either neutralize the phosphate or do a water extraction. I always did a water extraction on the 3rd pull and when it hit the alcohol as I combined them, it make a murky unappetizing mud cocktail..
THEN THERE WAS THIS ONE TIME I came across a HUGE HAUL of big laughing gyms (Gymnopilus spectacles at the time, but there was recently a lot of genetic work done on the genus that I haven't read) which are active in the US and bruise green, but the European equivalent Gymnopilus junonius isn't active. Anyway, I was poor at the time, but Gymnopilus are notoriously bitter, so I dried them in a dehydrator and did a water extraction on 45 grams dry ( eq. To 1 pound fresh) as they are not reported to be very potent. I layer there on the couch feeling like I was being stabbed all over my body with hot pokers for the first hour before I did have a fair trip equivocal to 3-4 grams of cubensis. Trying times, those were. UNFORTUNATELY I have more negative stories than positive ones about psilocybin mushrooms. I abused them too much. I would take them on a Tuesday and sit around the house and drink beer and watch TV. I tripped mushrooms probably 75 times the first year I was successful at cultivating them. I suggest saving the mushrooms for special occasions a few times a year AT THE MOST.
Extraction is definitely the way to go. Comes on in 20 minutes instead of waiting an hour. Mushrooms are high in chitosan, lobster armor. Which is hard to digest and could give you a belly ache, or diarrhea, Which sucks when you are tripping. Not eating the fruit bodies (sporocarps some say) is a great plan. A lot of people have tried strains of P.cubensis, which is easy to cultivate, but thr stronger woodloving species are much tougher and taste terrible. Like eating cat-piss soaked twigs. You gotta really want it, to choke down a few grams of those