$re = '/^([^,]*,(\d\d)_[^,]*,[^,]*)(?<!_\d\d),/ms';
$str = 'test,12_blah,blubb,anything
test,34_blah,blu_34,doesn\'t matter
test,56_foo,bar,nevermind';
$subst = "$1_$2,";
$result = preg_replace($re, $subst, $str);
echo "The result of the substitution is ".$result;
Please keep in mind that these code samples are automatically generated and are not guaranteed to work. If you find any syntax errors, feel free to submit a bug report. For a full regex reference for PHP, please visit: http://php.net/manual/en/ref.pcre.php