Froome, the Team Sky rider and Tour de France winner, was caught napping in the opening minutes of the mountainous 120 kilometres stage from Sabiñanigo to Formigal.

Eventual winner Brambilla launched the days first attack after three kilometres before a decisive attack by Spanish challenger Alberto Contador and his Tinkoff team-mates. 

Quintana's Movistar team launched a separate attack soon after to bridge the gap to the leaders, but Froome was left isolated and with most of his team-mates even further behind.

Froome remained between two and three minutes behind as they approached a summit finish.

Once there, Quintana attacked with a blistering acceleration.

Only Contador and Brambilla were able to match him, before the Spaniard was cut adrift to leave a two horse race.

Brambilla crossed the line in 2hours 54min 30sec to win by three seconds ahead of the Colombian.

Another Italian in Fabio Felline crossed the line third, 25 seconds behind, as Contador crossed seventh.

Froome came home 2:40 behind to remain in second place behind Quintana overall.

But he now sits 3:37 behind, 20 seconds clear of third placed Colombian Esteban Chaves.

Tomorrow's stage will consist of a 156.4km flat journey from Alcañiz to Peñíscola.