British number three James Ward could not build on his run through qualifying as he lost to Turkey's Marsel Ilhan in the first round of the Barcelona Open.
The Londoner, 28, had won two matches in qualifying on the clay but went down 7-6 (7-2) 3-6 6-1 against Ilhan, ranked 22 places higher at 84th in the world.
Russian 17-year-old Andrey Rublev, the junior world number one, upset 34th-ranked Fernando Verdasco 7-6 (7-4) 6-3.
Japanese top seed Kei Nishikori plays Teymuraz Gabashvili on Tuesday.
Spanish second seed Rafael Nadal, trying to win his ninth Barcelona title, will begin his campaign later in the week against Nicolas Almagro or Paolo Lorenzi.