Flame-orb is good with Pokemon with Guts. Because Guts boosts Attack if there is a status problem and Flame-orb does less damage than Toxic-orb. Note: The Attack boost still comes! The Burn Attack drop does not occur at all, this is a common misconception.
It is also good for Pokemon with Quick-feet who are special Attackers.
It also can be useful for Pokemon with Magic-guard as it prevents then from being paralyzed, it is also a common strategy for Sigilyph to use this and Psycho-shift to pass on the Burn. The Flame orb is better because Veno-shock would do double damage if it was the Toxic-orb.