The slow left-armer, who had managed only six wickets in his previous 17 Tests, helped dismiss India after tea despite the home side winning the toss.
Murali Vijay top-scored with 75, while leg-spinner Imran Tahir claimed 2-23.
South Africa struggled to 28-2 in the 20 overs possible before the close, with opener Elgar unbeaten on 13.
Off-spinner Ravichandran Ashwin, opening the bowling, trapped Stiaan van Zyl lbw for five before Faf du Plessis - also playing no shot - was bowled by Ravindra Jadeja.
Nine of the 12 wickets in the day fell to spin, with Vijay - lbw attempting to sweep Simon Harmer - part of a collapse from 102-3.
"This is not a good Test pitch wicket though it's a result-oriented one," said Elgar. "We sort of expected it to play like that but we didn't expect it to crumble so early.
"It was right up there with the hardest ever Test cricket I've played. Let's hope that it backfires [on India] and turns out to be a great victory for us."
India's batting coach Sanjay Bangar responded: "It's a very challenging wicket where run-making is not easy.
"It says 201 runs on the scoreboard but it's worth far more. But I think runs can be made on this wicket as Vijay showed. It's going to be a test of patience both for batsmen and bowlers."
This Test is followed by matches in Bangalore, Nagpur and Delhi.

Despite being relegated to League One, Mowbray says that he has the backing of Blackburn's owners, Venky's.
"They've been very supportive and I think they are going to give us some financial support, to ensure that we have a very strong season next year," he told BBC Radio Lancashire.
"They are basically telling me that those decisions will be mine. There is no pressure to sell any players."
Mowbray replaced Owen Coyle as manager at Ewood Park in February, but could not save Rovers from being relegated from the Championship on the final day.
The 53-year-old has experience of managing in the third tier having been in charge at Coventry City before Blackburn.
"What I know now is it's a really difficult league," he added. "There are some big strong powerful men in that league. It's a job for men, not for boys, which I found out at Coventry City."

The 34-year-old joins the county as cover for fellow West Indies paceman Fidel Edwards, who broke an ankle while playing football last week.
Best has played 25 Tests and 26 one-day internationals for his country, and taken 316 wickets in 115 first-class wickets at an average of 28.
Like Edwards, he is a Kolpak signing, with South African Ryan McLaren Hampshire's designated overseas player.
"Tino trained with us in Barbados during pre-season and looked good," Hampshire director of cricket Giles White said.
"It's come about at short notice, initially on a short-term contract. He seems excited about the opportunity and very motivated to do well."
Best will play for Hampshire in a three-day second XI match against Somerset at the Ageas Bowl starting on Monday with a view to joining the first-team squad for the County Championship game that begins against Middlesex on Sunday.
As well as Edwards, who will undergo surgery on Tuesday, Hampshire are currently without the services of bowlers Reece Topley, Gareth Berg and Ryan Stevenson through injury.
Ireland seamer Craig Young has also joined the county on a short-term loan deal.
"We'll support Fidel through his recovery and look forward to having him back in a Hampshire shirt as soon as possible," White added. "He's a class act and the team will miss him."
Part-time spinner Dean Elgar took 4-22 as South Africa bowled out India for 201 in Mohali, on the opening day of the four-Test series.
[NEXT_CONCEPT]
Blackburn manager Tony Mowbray says he is under no pressure to sell players.
[NEXT_CONCEPT]
Fast bowler Tino Best has joined Hampshire on a short-term deal.