I want to add in Bitch...Jerk, but that's really from a lot of seasons.
Supernatural 2: Why is it our job to save everybody?
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S1, "Wendigo," Dean: I think he wants us to pick up where he left off. You know, saving people, hunting things—the family business.
Where does it first happen, Perkins?
Some more S5:
5x20: Crowley: Where's your moose?
5x17: Castiel's voicemail: You have reached the voice mail of [Castiel: I don’t understand. Why do you want me to say my name?]
5x20: Dean: All those angels, all those demons, all those sons of bitches, they just don't get it, do they Sammy?
Sam: No they don't, Dean.
Dean: You see, Brady, we're the ones you should be afraid of.
There's the one from Dream a Little Dream
Dean: Bitch.
Sam: What?
Dean: uh... you're supposed to say jerk.
That's from What Is and What Should Never Be, isn't it, Laga?
eta: supernaturalwiki has it like this:
Dean: Bitch.
Sam: What are you calling me a bitch for?
Dean: You're supposed to say jerk.
Sam: What?
Oh you're right, ita.
Where does it first happen, Perkins?
I don't know. I will try to find out though.
First "bitch, jerk" is in the pilot in John's motel room.
That's my other problem- trying to remember exact quotes. I found this exchange on imdb
5x14
Dean: This is a fight? Are we in a fight?
Castiel: This is... their handshake.
Dean: I don't like it!
Castiel: No one likes it.
S4 4x2 Castiel: You should show me some respect. I dragged you out of hell. I can throw you back in.