select users.username
from relationships
inner join users on relationships.user_2=users.id
and relationships.user_1=2;
you will need to use this in your database. you just change the code at the end (relationships.user_1=2) with your session user id :)
edit: to get it all In one query. I also added a row for status (blocked, friend, pending request):
SELECT users.username
FROM relationships
INNER JOIN users ON ((relationships.user_1 = users.id AND relationships.user_2='$user')
or (relationships.user_2 = users.id AND relationships.user_1='$user'))
and relationships.status=1