Indian spinners Ravichandran Ashwin (2-21) and Pragyan Ojha (1-3) gave the touring side's batsmen early problems after the hosts continued to pile on the runs for most of the day.
Resuming on 323-4, Cheteshwar Pujara (206 not out) and Yuvraj Singh (74) moved their fifth-wicket stand on to 130 before the former hit a low full toss off Samit Patel to wide long-on just after lunch.
Pujara lost three more partners but went through to a largely untroubled maiden double century off 374 balls (21 x 4) before India declared on 521-8.
Graeme Swann was by far the pick of the England bowlers with 5-144 but the lack of a front-line spin partner cost the visitors dearly.
India made no such mistake, giving off-spinner Ashwin the new ball and then introducing slow left-armer Ojha soon after.
Nick Compton (9) laboured through 53 balls on his Test debut before Ashwin spun one through the right-hander's defences.
Nightwatchman James Anderson and Jonathan Trott fell in successive overs to bat-and-pad fielders before Kevin Pietersen (6 not out) held on with skipper Alastair Cook (22 not out) until the close.
