$re = '/\\\\\\\\[^. ]*\K|(?!^)\G\.([^. ]*)/i';
$str = 'A.B.C.\\\\valid.A .\\\\valid.A.B.C .\\\\valid.X.Y.Z .p.q.r.s ';
$subst = "?$1";
$result = preg_replace($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