Вместо INSERT .... VALUES
, который не допускает предложение WHERE
, используйте INSERT .... SELECT
:
$stm= "INSERT INTO `orders` (userid, username, quantity, time, image, uprice, tprice)
SELECT :userid, :username, :quantity, :timee, :image, :uprice, :tprice
WHERE NOT EXISTS (select username from orders where username=:username and image=:image)";