I find it very interesting that people who consume alcohol get less shy.
Therefore my question:
Why does drinking alcohol reduce shyness?
And are there any other (legal or illegal) substances who have such an effect on the human brain?
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It has to do with the excitatory affect alcohol has on almost all neurotransmitters and their receptors, including serotonin, dopamine, and GABA.
Very, very broadly:
Serotonin: Generally makes one seek a human connection.
Dopamine: Motivation to do things that are stimulating, like conversation.
Gaba: Surpresses anxiety.
GHB will do this even more - but it may do it to way too much of an extent. (Mostly Gaba, but increases tyrosine hydroxylase as well which = more dopamine.)
MDMA obviously (it causes your serotonin receptors to instead of soaking up the neurotransmitter pump them out).
Amphetamines to an extent. (Similar to the last two)