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For dragons to breath fire is certainly possible to have happened. Today fireflies produce light, eels produce electricity and the bombardier beetle can produce fire. The bombardier beetle has a canon near his rear end where he can blast his enemies with chemicals that are 212 degrees Fahrenheit: the temperature of boiling water. How does the beetle do that? This beetle has compartments where he stores fiery chemicals. When these chemicals unite they explode. If a tiny beetle can possess such a sophisticated mechanism in its rear, then a dinosaur or dragon could also have had a similar mechanism that would allow it to breathe fire to defend itself.
In fact, some of the dinosaurs have compartments in their heads that are connected to their nasal passages. The Tyrannosaurs Rex has a head the size of a car but his brain was the size of a baseball. The rest of his head was full of these compartments connected to his sinuses. If he had these special chemicals stored in these hollow compartments, it is possible that he could have been a fire breathing dragon.
In addition, legends of fire breathing dragons have circulated around the world for centuries and throughout history. They are depicted in artwork and literature. Almost all cultures have dragon legends despite having had no contact with each other.
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