The usual reason for organic working fluids is the low heat of vaporization, folks figuring that if it is easier to boil, it makes for a better engine.
Of course, Sadi Carnot said that theoretical maximum efficiency is equal to 1 - (cold reservoir temperature / hot reservoir temperature), which obviously means that potential efficiency rises as you increase the temperature of the working fluid...so a fluid that vaporizes more readily isn't naturally your best bet. More to the point, organic fluids tend to break down well below the temperatures at which many steam systems idle along, so efficiency is not a strong suit.
Another problem is that these low boiling point fluids usually ALSO have low specific heat content, maybe from 1/4 to 1/2 half that of steam, which means you need to pump a lot more fluid to produce the same work...leading to much higher feed pump losses than a steam plant sees.
Another issue is that the Mollier tables for such fluids shows that quite often the fluid goes into superheat when the exhaust releases, which amounts to a lot of wasted energy unless a very exhaust heat exchanger is fitted.
Then there is the cost, water is kinda cheap, even if you splurge on demineralized, deionized and buffered feed. If you spring a leak and lose your water, it is readily replaced. Organic fluids, much less so. And the safety factor, unless the steam is so hot that it will scald your lung tissues, a little steam vented into the working area just tends to soothe the sinuses; a lot of these organic chemicals qualify as a Hazmat condition.
Admittedly there is a place for organic working fluids, this being when you have a LOT of lower level heat that you want to exploit, usually said heat being a by-product of some industrial process although there has been a lot of ongoing work in OTEC applications. These systems will not be very efficient, so they start to pay as size goes up and scale factors become favorable. The technical challenges are much higher to prevent working fluid losses and decomposition. I don't really see this being suitable for the average backyard workshop unless maybe you have an old Ofeldt Naptha launch sitting around and are just dying to run it...and I admit the idea of boiling gasoline in a tank and piping it to an engine makes me a tad nervous...
Ken