Seeds Kiki Bertens and Laura Siegemund suffered first-round exits at the Generali Ladies Linz on Monday.
Dutchwoman Bertens, seeded sixth, suffered a 6-4, 6-2 defeat to Romanian Sorana Cirstea, raked 60 places below her. Bertens led 4-3 in the first set but suffered two breaks as Cirstea won three straight games to move ahead.
Viktorija Golubic claimed her first win over Siegemund at the third attempt, taking 95 minutes to see off the eighth-seeded German 6-4, 6-2.
There was joy for fifth seed and defending champion Anastasia Pavlyuchenkova, however.
The Russian required less than an hour to dispatch of Latvian Anastasija Sevastova 6-4, 6-1 and advance to the second round.
The other first-round clash saw Misaki Doi fight off Johanna Larson 7-5, 3-6, 6-1.
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