$re = '/(?!<span class=\"myclass\"\>.*)(\{\{.*?\}\})(?!.*<\/span>)/U';
$str = '<span class="myclass">{{$$x = {-b \\pm \\sqrt{b^2-4ac} \\over 2a}.$$}}</span>
<p>{{$$x = {-b \\pm \\sqrt{b^2-4ac} \\over 2a}.$$}}</p>
<p>{{any text}}</p>';
preg_match_all($re, $str, $matches, PREG_SET_ORDER, 0);
// Print the entire match result
var_dump($matches);
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