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Resuming on 21 for two, the visitors lost wickets at regular intervals with India making the most of foggy morning conditions at the Feroz Shah Kotla Stadium.
India's nemesis Shivnarine Chanderpaul (39), who hit a century in the first innings, and skipper Darren Sammy (8) were batting at the break with West Indies stretching their overall lead to 204 runs with three wickets in hand.
Overshadowed so far by the spinners, Ishant Sharma bowled with real fire and overnight batsman Kirk Edwards (33) was lucky to survive a strong leg before appeal in the first over.
Sharma returned to remove Fidel Edwards for one caught behind and nearly had Darren Bravo (12) in the same over too but Ashwin dropped the catch at extra cover.
Fellow quick Yadav claimed his maiden test wicket when he uprooted Kirk Edwards' off-stump after the batsman offered no shot.
Ashwin more than made up for his fielding lapse with a double-wicket maiden over, trapping Bravo leg before and then pegging back scoreless Marlon Samuels' off-stump to reduce West Indies to 63 for six wickets.
Yadav removed Carlton Baugh (7) for his second wicket of the match before Chanderpaul put his foot down to frustrate the Indians.
