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Real Madrid 4 Barcelona 1
Despite a fairly even start it was the champions who drew first blood with Raul's first-time finish beyond Victor Valdes opening the scoring with just 13 minutes played.
Barca's defending did not get any better from there with Arjen Robben unmarked from Guti's pin-point free-kick to double Real's lead with less than a quarter of the match played.
Barcelona coach Frank Rijkaard tried to mix things up a bit and he opted for an early change in whipping off Eidur Gudjohnsen and replacing him with Giovanni Dos Santos.
The home side continued to pile on the pressure before half time with Robben and Raul both going close to heaping more embarrassment on out-of-sorts Barca.
Things failed to improve for the visitors after half-time with second half substitute Gonzalo Higuain scoring with deft chip over Valdes following a fine square-ball by Mahamadou Diarra.
Barca tried to respond, but even when Thierry Henry was given time and space outside Iker Casillas' penalty area he could only drag his effort wide.
Fine save
Only a fine save from Valdes kept the score down after Marcelo cut inside on his right foot and unleashed a fierce drive at the visitors' goal.
A fourth did arrive when substitute Ruud van Nistelrooy stroked the ball home from the penalty spot after Carles Puyol was harshly deemed to have handled Robinho's fierce shot.
Barca did get on the scoresheet when Henry beat the offside trap before curling a delightful shot beyond Casillas.
The game ended on a sour note for Rijkaard's side when Xavi was needlessly sent off in injury time for collecting his second yellow card of the game.
The heavy defeat means Barca cannot displace Villarreal in second spot, so the Catalan giants will have to go through the qualifiers to reach next season's UEFA Champions League.