$re = '/<(?![^>]*<)/i';
$str = '<!DOCTYPE html>
...
<anytag>
<h1>This is the less than < symbol. </h1>
<h1>This is the less than or equal to <= symbol. </h1>
</anytag>';
$subst = "<";
$result = preg_replace($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