Of course not, and their T&C's say: "None of these Carriage Conditions will annul any available right to which applicable legislation entitles the Passenger."
However as Regulation 261 does not apply to change of schedule s/he has no rights under it. However that does not mean that s/he has no rights. Contract law may have been breached.
I note that
Vueling's T&C's do not carry the regular exclusion that the schedules do not form part of the contract (based on the IATA Recommended Practice), so perhaps one could argue that Vueling's failure to state that explicitly the schedule does form part of the contract.
Have you considered contacting the Spanish NEB for their views?