Run machine Graeme Smith withstood an early James Kirtley attack, then fell to one of the more bizarre dismissals in Test cricket.
Sussex star Kirtley was handed the new ball on his debut and produced a lively opening spell as England maintained their stranglehold of the second Test with South Africa.
Kirtley finished the day with 0-21 from ten overs, of which three were maidens.
He had a very good leg-before shout against Herschelle Gibbs turned down in his first over as England defended their first innings score of 445.
It was Andrew Flintoff, however, who got rid of Smith.
The touring skipper had added 35 to his series total of 621 when, attempting to clip a delivery from Flintoff off his hip on to the on-side, he hopped backwards and stood onto his stumps.
With Gibbs having departed five overs earlier, playing on attempting to drive Steve Harmison, it was a major breakthrough for England with South Africa reaching 84-2 by the close on a deteriorating pitch needing a further 162 runs to avoid following on.
Kirtley's first ball in Test cricket was swotted just past the hands of mid-wicket for four by Gibbs but the Sussex man responded well to his uncertain start and gave Smith some early alarms.
Earlier England had struggled to build on the strong foundation given to them by their upper order batsmen on the opening day.
Resuming on a commanding 272-3 with former captain Nasser Hussain and newcomer Ed Smith both well set, they were hoping for a total of around 500 to put the pressure on South Africa for the first time in the series.
South Africa, though, had clearly learnt from their opening day experience and were far more disciplined in their approach and earned their reward as a result with England's middle order crumbling.
England's overnight batsmen both fell inside the first 13 overs of the day, with Hussain adding only eight runs to his overnight 108 before being trapped leg before to a Shaun Pollock delivery which cut back into his pads.
He was soon joined by Kent batsman Smith, who fell five overs later when he edged all-rounder Jacques Kallis behind having scored a determined 64 in his maiden Test innings.
Those dismissals were the start of a middle-order collapse with Flintoff falling for a duck five overs later, edging Andrew Hall to slip after 29 minutes at the crease trying to get off the mark.
Ashley Giles continued his impressive form with the bat this summer by contributing a useful 22 but was bowled through the gate by Hall, leaving veteran Alec Stewart with the responsibility of taking England past 400 and beyond.
Stewart relished the challenge and hit a gutsy 72, which included 11 boundaries
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