Since MIDI works via a current loop, splitting the MIDI Out at the SOCKET probably won't work very well, both receivers would be sharing the current, and the optocouplers would get half the current or one would rob the other or some other weirdness... can't be sure exactly.
It would be best to add a buffer (logic gate), fed from the point driving the MIDI Out... in a MIDIbox "Core" this would be the Tx pin of the PIC, between the 220 ohm resistor and the MIDI Out pin. Then the output of the buffer goes to 220 ohm resistor to the replicated MIDI Out socket. Remember that as the signal is high and low, it is sinking current from the other MIDI Out pin (connected to 5V via 220R), out the cable, through the receiving end, returning back in along the cable to the MIDI Out pin. So you replicate this bit too around the buffer.
I have actually tried this with just a BC557 instead of a buffer (made a MIDI Thru by connecting BC557 to Rx pin of PIC).
So unless you are planning to switch between the two, you do need some kind of buffer... or at least tap directly to the Tx pin or whatever is driving the MIDI and replicate the whole 5V->220R->socket->220R->Tx pin arrangement.