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Vinci defeated the top-seeded Dane 6-4, 7-5 to reach the third round. Wozniacki, playing her first tournament since Bastad in the first week of July, had enjoyed a first-round bye.
After dropping the first set, Wozniacki mounted a challenge,taking a 5-1 lead in the second.
But Vinci, ranked 22 in the world, battled back to finish off the victory.
"This is the best victory in my life," said Vinci, 28. "I was 5-1 down but I knew that I can win the set because it was a lot of wind, so some mistakes.
"I tried to stay focused and play aggressive."
Wozniacki, winner of a WTA-leading five titles this season, had trouble with her serve in the windy weather. The conditions contributed to her seven double faults.
"It was very difficult at first with the wind," Wozniacki said. "Especially when you threw it up. It was going everywhere,so definitely that didn't make it easy. It was blowing in different directions, but it's the same for both players."
She was particularly disappointed that she couldn't at least win the second set to give herself a chance in a third.
"I would have liked to have won that one and especially after leading 5-1 in the second," Wozniacki said.
Her early exit leaves the tournament without its top two seeds after second-seeded Kim Clijsters retired from her match against China's Zheng Jie with a stomach muscle injury that casts doubts on the Belgian's upcoming US Open title defence.
Wozniacki and Clijsters led a strong field that included all
of the WTA's top 20 players here this week.
But one of the players most in the spotlight isn't even in that group, as Serena Williams arrived unseeded in the wake of her 11-month injury layoff that ended in June.
The former world number one defeated Germany's Julia Goerges 6-1, 7-6 (9/7) to set up a meeting with Zheng.
Williams also said the gusty wind made things difficult.
"It was just so much wind out there so it was a little difficult, but we were in the same circumstances so that's what I tried to think of," she said, adding that she had to tone down her powerful serve.
"I had to hit it softer today because it was so windy, I had to take pace off my ball," she said. "If you hit it too hard the ball is going to totally fly the harder you hit."
Third-seeded Vera Zvonareva, fourth-seeded Victoria Azarenka and fifth-seeded Maria Sharapova all advanced, as did French Open champion Li Na and Wimbledon champion Petra Kvitova.
Zvonareva defeated fellow Russian Nadia Petrova 7-5, 6-4,while Sharapova survived some erratic serving in the second set to defeat Serbian qualifier Bojana Jovanovski 6-1, 7-5.
Azarenka, of Belarus, ended the hopes of Canadian Stephanie Dubois 6-0, 6-0.
China's Li advanced on a walkover when compatriot Peng Shuai withdrew prior to their match with a left hip injury suffered in San Diego last week.
"It is sad for her," said Li, the sixth seed. "Always tough when you're playing same-country player. We train together, we know much (about each other). Always tough."
Kvitova reached the third round with a 7-6 (7/3), 6-3 victory over Spain's Anabel Medina Garrigues.
The seventh-seeded Czech came back from 5-6 in the first set, firing two aces past Medina Garrigues to make it 40-15.
The 33rd-ranked Spaniard then netted a ball to send the set to a tiebreaker.
Kvitova shrugged off a rain delay in the second set to secure the victory.
Eighth-seeded Francesca Schiavone of Italy also reached the third round with a 6-1, 6-3 victory over Ekaterina Makarova.
Posted in: Tennis: Vinci topples top seed Wozniacki
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