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episode 213
well goku fights in an episode called "Battle for the Universe Begins" in the uncut series it's episode 279 that they start in and if I'm not mistaken its episode 280 in the uncut version were vegeta fights buu and the episode is called "Vegeta's Respect".
yes when krillin gohan and vegeta teamed up to defeat frieza that's when they became friends but vegeta is always getting mad at him for some stupid reasongoku and vegeta actually become friends after they killed kid majin buu. even after they defeated freeza vegeta's ultimate goal was to kill goku and become the strongest, but he was forced to team up with goku on other accounts although he disliked itIn the end Vegeta was able to accept Goku and develop an affection for him. Goku had always been nice to Vegeta and Vegeta has on a couple of occasions, risked his own life to protect Goku, if he needed it or not.Yes after Goku defeat Vegeta and let him go,Vegeta and Goku become BFF
on mega video episode 230
If you are talking about Vegeta as a kid, I have seen him fight in the movie-Bardock-the Father of Goku (if i remember correctly). If you are talking about Vegeta Jr. (the great-grandson of vegeta), he is seen fighting Goku Jr. in the last episode of Draghon Ball GT.