FR 9601 then FR 572 at Madrid
Rome → Madrid → Porto
Timetable, Madrid time
21:20FR 9601 from Rome at the gate
16:40FR 572 to Porto leaves the gate
19 h 20 apart on the timetable, overnight
FR 572 leaves 19 h 20 after FR 9601 arrives on the timetable: more than half a day, so not a connection we count.