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The main phenomenon behind this is- EVAPORATION CAUSES COOLING.
Stuff like alcohol, perfumes etc when rubbed on skin, actually evaporate turning into vapours. This is because evaporation causes cooling. Alcohol and perfumes evaporate at room temperature.
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Evaporative cooling Any object will absorb heat from its surroundings if the surroundings are warmer than it. Since room temperature is usually lower than body temperature, alcohol is usually colder than your skin. When you put alcohol on your skin, first, your body will warm the alcohol until it is the same temperature as your skin, and that feels a little cold to you (just like when you touch any object at a lower temperature than body temperature, like a piece of metal). 
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