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No. Chloroform has to get into your blood via your lungs when you breathe it in.
There is no quick, easy, safe way to knock someone unconscious. Restricting airflow will keep someone unconscious for as long as the airflow is restricted. And if you’re unconscious for more than a few seconds (and it wasn’t a carefully administered sedative) you might well die. Like Archer says “Hahah, that’s really bad for you!”
So I guess you have to mix it with something else for them to stay asleep? I hear chloroform takes a long time to work, so maybe you can apply that while you hold them?