Why this last unconstrained path?

Clock sources (includes generated clocks such as PLL clocks) are startpoints of timing paths. Timing exceptions (e.g., set_max_delay) cannot be applied "across" a startpoint.

The set_max_delay is from the input clock port to the output clock port, which passes across the PLL clock. This means your set_max_delay exception was ignored. If you call report_timing with the exact same -from/-to arguments and you should see zero paths reported. You can also use report_exceptions to verify your exceptions (Quartus II 9.0 and newer).

Instead try simply (dropping the -from):

set_max_delay -to [get_ports Clk33_Out] 12

or:

set_max_delay -from [get_clocks name_of_pll_clk] -to [get_ports Clk33_Out] 12

You'll also need a set_min_delay to satisfy hold timing.