My spreadsheeting pleasure...
I can't decide if I should include what Dean says to Sam as he dies from AHBL1, but this is for sure:
2x22: Dean: When you were little, couldn't have been more than five, you just started asking questions. How come we didn't have a mom? Why did we always have to move around? Where's Dad? I remember I begged you: "Quit asking, Sammy. You don't want to know." I just wanted you to be a kid, just for a little while longer. Always tried to protect you. Keep you safe. Dad didn't even have to tell me. It was just always my responsibility, you know? It's like I had one job. I had one job, and I screwed it up. I blew it, and for that, I'm sorry. I guess that’s what I do. I let down the people I love. You know, I let Dad down, and now I guess I’m just supposed to let you down, too. How can I? How am I supposed to live with that? What am I supposed to do? Sammy? What am I supposed to do?
God, I can't even read that quote without hearing JA's voice break and the Texas slipping in.
I want to add in
Bitch...Jerk,
but that's really from a lot of seasons.
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?
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.