The term "ass-butt" has become widely used in fandom as a term of both abuse and affection. Ass is known as another word for a donkey. Castiel could have called Lucifer a donkey's butt.
As Dean is confronting Michael and Lucifer, to try and reach Sam, Castiel calls out "Hey, ass-butt!" at Michael (much to Dean's confusion) before throwing a a molotov cocktail of holy oil at him, giving Dean his five minutes alone with Lucifer. Unfortunately Castiel is soon blown up by Lucifer for his troubles.
'Ass-butt.' I-I-I still don't get that.
When Lucifer takes Sam to revisit some memories, he takes them to Stull Cemetery to the moment when Castiel molotoved Michael. Lucifer admits to Sam that he still does not understand what "ass-butt" means, before Sam moves the conversation along. Later, when Dean and Castiel arrive to save Sam from the beating Lucifer is inflicted on him, Cas again uses the insult to get Lucifer's attention.