Angelique Kerber made a shock exit in Doha after losing in straight sets to Saisai Zheng 7-5 6-1.
The Australian Open champion had a day to forget after losing a tight first set 7-5. After holding to love in the first game of the second set, the world number two went on to lose six games in a row to make an early exit.
Playing her first tour match since beating Serena Williams, the German would have hoped to build on her first slam with a deep run in Qatar.
Halep heading home
Continuing an unpredictable 2016 for the WTA, Simona Halep bowed out in straight sets to Elena Vesnina.
Losing 6-7(1) 6-4 6-1, the Romanian's miserable season went on after looking to have won the match being 7-6 4-1, Halep saw an almighty collapse as she went on to lose 11 of the next 12 games. With a lot of points to defend, Halep will be concerned as she looks to be dropping out of the rankings.
Best of the rest
Agnieszka Radwanska continued her great form as she dispatched of Katerina Bondarenko 6-4 6-4 to seal her 11th win of 2016. Playing some great tennis, the Pole moved onto the next round as she maintained her resurgence since winning the year end championships in 2016.
Petra Kvitova had a confidence boosting win as she defeated last weeks Dubai finalist Barbora Strycova 7-6(2) 6-4.
Caroline Wozniacki also won as she beat Daria Gavrilova in a much needed win for the Dane, winning 6-3 6-3.
Roberta Vinci celebrated making her top ten debut with another win as she defeated Daria Kasatkina 2-6 6-4 7-6(3).
Her fellow compatriot Sara Errani lost to Timea Babos 6-4 6-1.
Carla Suarez-Navarro def. Donna Vekic 7-6(5) 6-4
Eugenie Bouchard def. Denisa Allertova 7-6(0) 7-5
Andrea Petkovic def. Margarita Gasparyan 6-3 6-3
Timea Bacsinszky def. Yulia Putintseva 6-2 7-6(0)
Jelena Ostapenko def. Svetlana Kuznetsova 7-6(5) 6-0
Monica Niculescu def. Jelena Jankovic 3-6 6-4 7-5
Coco Vandeweghe def. Belinda Bencic 6-4 6-2
Cagla Buyukakcay def. Lucie Safarova 7-6(8) 7-5
Garbine Muguruza def. Nao Hibino 6-2 6-0