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Kakashi"s first known usage of the Mangekyo Sharigan was versus Deidara. However, i think your inquiry really is why did the not use it earlier. There can be a variety of reasons why the did not usage it or to be not displayed using the earlier.
Kakashi awakened the Mangekyo Sharingan when Rin was killed. He for this reason failed to store his promise come Obito. Hence, this to be a emotionally painful minute for him, tied come both Rin and also Obito. Maybe he walk not desire to usage it since to prevent revisiting those emotions.
As stated in lexter"s answer, another reason is the being a non-Uchiha, he just did not have enough stamina to usage it properly in battle. Also after timeskip, he could only usage it double in a day, and had to take remainder for a mainly or for this reason after he used it. Prior to timeskip, he was in charge the genin-level students, and also he couldn"t risk acquiring knocked out and put his students in danger.
Also, before the timeskip, he just did not gain to hit villains versus whom he was required to usage it. That only battled Zabuza and also Haku during the land of tide arc, and unnamed shinobi indigenous Sand village and Sound village during the invasion of Konoha arc. If Orochimaru were to hit him, Kakashi would probably be driven to using it, however Orochimaru combated with the third Hokage instead.
Losing come Uchiha Itachi quickly may have actually compelled Kakashi to think about using it, due to the normal shounen/Naruto reasonable of "If I desire to defend my nakama, I have actually to obtain stronger."
There could also be a couple of author issues why Kakashi couldn"t be presented using the earlier. Sasuke was a protagonist at the time, and also his main aim in life was to death Itachi. Therefore, that was crucial to present Itachi together a superpowerful villian. Ensuring the Mangekyo Sharingan is first mentioned once Itachi is introduced would maximize the audience"s perception of how solid and evil Itachi is.
The other reason is it was not in the author"s arrangement that Kakashi had currently awakened the Mangekyo Sharingan as soon as the series started, and also planned to market an alternative explanation for how he awakened it during the timeskip period.
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However, as he began addressing the hanging threads when winding up the story, he determined to shoehorn it into Obito"s backstory.