In addition to Tushar's answer to make it work when numbers_mst is empty:
SELECT random_num
FROM (
SELECT FLOOR(RAND() * 99999) AS random_num
UNION
SELECT FLOOR(RAND() * 99999) AS random_num
) AS numbers_mst_plus_1
WHERE `random_num` NOT IN (SELECT my_number FROM numbers_mst)
LIMIT 1