In Pokemon emerald there is the Battle Frontier. Perhaps in the far left region of the island you will see a cabin with a red roof and such. Go inside and you would see two old ladies. They are both move tutors and the one on the right can teach your Pokemon fire punch and all other punches. It is worth 48 bp so have enough bp to buy it for your Pokemon.
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The only way Alakazam can learn Fire Punch is through a Move Tutor on Pokemon Emerald Version.
fire punch
No, Flareon cannot learn Fire Punch
You can only "learn" Fire Punch in Diamond via breeding a Pokemon with another who already knows Fire Punch (Magmar for example)
Darumaka learn fire punch at level 22Hope I helped