I generally encourage my weaker pupils to get into the habit of always converting to improper fractions at the start, and then back at the end. If a child has a good grip on maths, then they get to the point of being able to spot when they need to, and when they can just deal with the whole numbers first and then the fractions (which is certainly easier for those questions where you can just do that simply). But too many of them don't recognise that for questions like 4 1/3 - 2 1/2, you can't do it quite as simply as that.
In those cases, I find many pupils struggle with the idea of 'borrowing' from the whole number and/or get confused about which way around subtraction goes and so don't recognise that they need to. (i.e., the common mistake they make is to do 4 - 2 = 2, and then 1/3 - 1/2, convert that to 2/6 - 3/6, and then decide that is 1/6, rather than realising that as it's the wrong way round, they need to borrow from the whole number).
I think because subtraction is so often taught using a number line, going from the smallest number to the biggest number, some children don't always see it as 'taking something away from the biggest number', and therefor are more prone to thinking things like 2 - 5 is 3, because in their minds, it means 'going from 2 to 5 is three jumps'. This can sometimes cause problems when doing subtraction in a more conventional written format (e.g., column subtraction) or examples like here, with fractions.
So it is sometimes easier for older children who are being taught these more formal, written methods, are simply need to get the right answer, to just learn the rule that they should always convert to improper fractions.
For my younger pupils, it's sometimes helpful to go back and teach fraction subtraction on a number line as well: so 4 1/3 - 2 1/2 becomes 1/2 (up to 3) + 1 (up to 4) + 1/3 (up to 4 1/3). Then they still have to add fractions at the end, but many are more comfortable with that.
And of course I keep reviewing the idea of subtraction on a number line (counting up) meaning the same overall as subtraction by taking away, so that hopefully when they are older, they won't have the confusion of 2-5 or 5-2.