My theory: Seems to be a pressure thing. With the pot at min, the increase in pressure when hot is containable. When higher, the smaller volume of air in the top of the pot will cause a higher increase in pressure, forcing the coolant out somewhere.
This should not happen as the valve in the pressure cap should maintain pressure regardless of volume in the pot. Might need a new cap, although my experience is that usual failure is a loss of pressure rather than an increase.
But, as above, we need to know where it is leaking out. This will help us determine the cause, and therefore a solution. Don't we all love a puzzle? Although much easier when it is not yours.