Seeded third, Bopanna and his Canadian partner Daniel Nestor were shocked by Spanish duo of Rafael Nadal and Pablo Carreno Busta in straight sets, losing 6-7(3), 4-6.
There was more heartbreak stored for India later in the day when veteran Paes and Germany's Andre Begemann were shown the door by American-Australian duo of Jack Sock and Bernard
Tomic.
Wildcard entrants, Paes and Begemann fought hard before going down 6-3, 5-7, 7-10 in super tie-breaker of the match in the $4,164,780 ATP 500 event.
Image: Leander Paes
Photograph: Getty Images