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Was there any logic or thinking behind the experiments performed by Cannizzaro, Beckmann, Gattermann, Koch etc.?

Did they thoughtfully perform experiments or just add any two reactants and luckily discovered the reactions which are known by their name today?

I meant to ask that in Physics all problems are treated mathematically and logically; But in case of Organic Chemistry, there are lot of exceptions to all statements which are made by Cannizzaro etc. It is said that if a single observation is against a scientific law; the law is abandoned and new perfect law takes its place. But it seems that Organic Chemistry is unaware of this and "perfect" statements are not part of it.

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Sometimes it was a lucky accident, sometimes there was a lot of math and logic going in the designing experiments. The organic chemistry of that era, though, was a lot more applied and empirical than the physics of today. They usually weren't setting out to find the absolute laws-of-nature governing chemistry, they were just trying to make better dyes, medicines, rubber, etc, and stumbled upon new phenomena along the way.

Further Explanation

Almost all these guys worked in Germany in the late 1800s, when chemical industry was the hot new thing (think of biotechnology in today's world). There was a lot of money to be made in making better dyes, medicines, rubber, etc, so people would hack/engineer the established methods for making that stuff, and see if the resulting products were any better.

For example:

Chemical A cures headaches really well, but causes nausea. Chemical B gives a little relief from headaches, but doesn't have any side effects. I bet I could make chemical C (which no one had ever made before), which has a structure that's sort of a combination of chemicals A and B, and maybe that will cure headaches with no side effects.

==> {made the chemical and did some tests to find out the structure}.

What the heck! This has a completely different structure than what I was expecting, it must have undergone a second reaction to rearrange itself.

==> {publish paper},{get famous},{people 100 years later question the logic of your experiments} :)

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The problem with organic chemical reactions is that they are hard. Organic molecules have many covalent and polar covalent bonds, which require much energy to break. Specifying which bond you want to break may require very specific chemical conditions. It usually requires various catalysts to speed up the reactions. So to determine exactly what organic reaction you want can be rendered "logical", but it usually requires a lot of experimentation, which may well be sped up by "luck". But once the experimental results have been replicated, you have a "logical" procedure for the future. It may have not involved mathematics, but it was proven by experiment, which is the ultimate criterion in science, even in physics!

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