As for why we sometimes have to check the charts: Well, for an example, I just took off "IFR" from Seligman, AZ a few days ago. Seligman doesn't have an IAP. Nor an ODP. Nor a tower, Nor anything. (Multicom.) Hence, nowhere to look up an Approach (or Departure) freq. It's uncontrolled airspace at the surface (that is, IFR is not being controlled), so I had to fly my way to a nearby intersection in controlled airspace and pick up my clearance with ABQ Center from there. To find the Center freq, I had to look on the IFR chart.
However, it turns out that Seligman is close the boundary between LA and ABQ Center. Had I been headed westbound, LA Center would have been the one to call.
Otherwise, I generally don't use FF around Arizona. Often times we're too low for RADAR coverage (6500', sometimes even 8500' is too low). When I am high enough for coverage and flying at night, then I might try to pick up FF from LA Center on the way back from CA to AZ. For that case, I have to look it up on the IFR chart too.
In the old days, when I didn't have electronic charts, and might not have had IFR charts with me for the route, I would call FSS and ask them what the freq was for Center. That still works too.
And one might need to look up a freq to get back on the air if one misdialed and hosed up during the chain of ATC handoffs. I hear that happening to Airliners a lot on Guard.
Of course, it would be easier to look up pertinent freqs on iFly if it had it. But, as above, for some airports, it's not always clear what the correct freq is.