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Vincenzo Nibali celebrates winning stage 19th stage of the 2015 Tour de FranceBryn Lennon/Getty Images

An angry Chris Froome accused Vincenzo Nibali of "unsportsmanlike" behaviour after the defending Tour de France champion accelerated away when the race leader stopped with a stuck wheel on the toughest Alpine climb on Friday.

Nibali, who went on to win Stage 19, said Froome tore into him verbally at the finish.

"He was very angry but that's his problem," the 2014 Tour winner said.

Froome said a stone or piece of asphalt jammed between his brake and rear wheel on the Col de la Croix de Fer climb, forcing him to pull up momentarily to unjam it. While Froome stopped, Nibali rode away.

Stopping short of saying Nibali should have waited for him, Froome said: "It was almost as if my mechanical (problem) provoked his attack."

At the finish, Froome added, "I told him exactly what I thought of him."

Nibali's win on the exhausting Alpine stage rescued what has otherwise been a disappointing Tour for the Italian.

There were also fireworks in the race and another spectator incident appearing to involve Froome.

On the stage's final climb to the La Toussuire ski station, Nairo Quintana launched his most sustained and telling attack against Froome, and this time got the better of the 2013 champion.

Showing for the first time at this Tour that he's not untouchable, Froome chose not to stay with the Colombian, his closest rival, as he accelerated away and started eating into the British rider's overall race lead.

Froome said he preferred to save energy for Saturday's last Alpine stage, which features two very hard climbs. So he rode steadily, limiting the damage, rather than hunt down Quintana, he said.

"He's still got very good legs," Froome said. As the Movistar rider powered away, Froome said he told himself: "'I don't need to panic but I do need to keep something in reserve."'

Froome's reduced lead of 2 minutes, 38 seconds over Quintana, down from 3:10 at the start, should still be enough to get the British rider through the last competitive day in the Alps before the final stage to Paris on Sunday, which is largely ceremonial and won't change the overall podium standings.

Still, the smaller cushion will force Froome to watch Quintana very carefully on Saturday and means he cannot afford a bad day on the two huge "Hors Categorie" climbs, meaning they're so tough they defy categorization.

The last of those, up 21 hairpin bends to the Alpe d'Huez ski station, is cycling's most iconic ascent and will be lined with screaming spectators, a thrilling finale to another spectacular Tour.

"It's the final test," said Froome.

"I'm in a great position," he added. "I can't wait to get up there."

The dispute with Nibali wasn't Froome's only problem on Friday.

TV images of the final climb appeared to show a spectator stepping into the road and spitting as the race leader sped past.

Froome said he didn't see the spectator but called his behaviour "appalling." Earlier in the Tour, Froome said another spectator threw a cup of urine at him and another punched his teammate Richie Porte.

"We are human beings," he said. "You can't come to a bike race to spit at people, or to punch them or to throw urine at them."

As for Nibali, the Italian said he didn't see that Froome had pulled up on the Croix de Fer, even though television images appeared to show him looking back over his left shoulder at the Team Sky rider before accelerating away.

Nibali said he was speaking to a teammate, not looking back at Froome, and that he always had planned to attack on that climb. The manager of his Astana team, Alexandre Vinokourov, defended him, saying: "Vincenzo doesn't have eyes in the back of his head."

Froome said: "It seemed to me that Nibali had the whole climb to attack but he chose the moment that I had a mechanical (problem) to make his move. And I've heard from other riders that he turned, could see I had a problem and then attacked."

"That, in my opinion, is very unsportsmanlike," he added. "It's not in the spirit of the Tour de France."

Nibali said he was "very disappointed" at the way Froome spoke to him at the finish with language "too hard and too unjust to be repeated."

He added that as far as he is concerned, no rule says other riders must wait when a race leader has an accident.

After fixing his bike, Froome rode furiously to catch back up with other podium contenders. But Nibali was long gone, chasing after French rider Pierre Rolland, who summited the Croix de Fer pass first.

Hitting speeds of 70 kph (45 mph) on the descent and shaving the edges of the bends, Nibali then caught Rolland and overtook him on the final climb to La Toussuire.

Sweat pouring off his legs, he rode solo to the finish, with the cross from the chain around his neck in his mouth at the end.

Riding with the No. 1 bib as the defending champion, Nibali has had a tough Tour, unable to match Froome. He started the day in seventh place, 8:04 behind.

But with the time clawed back on his winning ride, Nibali jumped to fourth place, now 6:44 behind Froome and possibly within sight of a podium spot. Third-placed Alejandro Valverde is 1:19 ahead of the Italian.

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