Octane rating has nothing really to do with "octane" molecules. It's a measurement of detonation resistance compared to a pure octane source. Ethanol has zero octane molecules in it. Propane which has a very high octane (and very low flash point as well) and no octane moledules in it.
Another property, probably more related to octane rating is the auto-ignition temperature. For gasoline it's up around 280C where diesel is down around 260 an ethanol at 360.