SELECT A.*
FROM default_relations_users A
LEFT JOIN default_relations_users B
ON A.id_user_rq = B.id_user_ap
AND A.id_user_ap = B.id_user_rq
WHERE B.id_user_rq IS NULL;
I loaded you sample data (I added an additional index)
mysql> use Reynierpm
Database changed
mysql> DROP TABLE IF EXISTS `default_relations_users`;
Query OK, 0 rows affected (0.00 sec)
mysql> CREATE TABLE IF NOT EXISTS `default_relations_users` (
-> `id_user_rq` int(11) NOT NULL,
-> `id_user_ap` int(11) NOT NULL,
-> UNIQUE KEY `rusers_rq_ap_idx` (`id_user_rq`,`id_user_ap`),
-> UNIQUE KEY `rusers_ap_eq_idx` (`id_user_ap`,`id_user_rq`)
-> ) ENGINE=MyISAM DEFAULT CHARSET=utf8 COLLATE=utf8_unicode_ci;
Query OK, 0 rows affected (0.05 sec)
mysql> INSERT INTO `default_relations_users` (`id_user_rq`, `id_user_ap`) VALUES
-> (1, 2), (1, 3), (1, 4), (2, 1), (2, 2), (2, 3);
Query OK, 6 rows affected (0.00 sec)
Records: 6 Duplicates: 0 Warnings: 0
mysql> select * from default_relations_users;
+------------+------------+
| id_user_rq | id_user_ap |
+------------+------------+
| 1 | 2 |
| 1 | 3 |
| 1 | 4 |
| 2 | 1 |
| 2 | 2 |
| 2 | 3 |
+------------+------------+
6 rows in set (0.00 sec)
mysql>
Here is the result of my answer
mysql> SELECT A.*
-> FROM default_relations_users A
-> LEFT JOIN default_relations_users B
-> ON A.id_user_rq = B.id_user_ap
-> AND A.id_user_ap = B.id_user_rq
-> WHERE B.id_user_rq IS NULL;
+------------+------------+
| id_user_rq | id_user_ap |
+------------+------------+
| 1 | 3 |
| 1 | 4 |
| 2 | 3 |
+------------+------------+
3 rows in set (0.00 sec)
mysql>
Give it a Try !!!
mysql> SELECT A.*
-> FROM default_relations_users A
-> LEFT JOIN default_relations_users B
-> ON A.id_user_rq = B.id_user_ap
-> AND A.id_user_ap = B.id_user_rq
-> WHERE B.id_user_rq IS NULL
-> AND A.id_user_rq = 1;
+------------+------------+
| id_user_rq | id_user_ap |
+------------+------------+
| 1 | 3 |
| 1 | 4 |
+------------+------------+
2 rows in set (0.01 sec)
mysql>