As has been stated in the comments, if you know that $A_n$ is simple for $n\geq 5$, and subgroups of index 2 are normal, you are done with that case.
For the $n=4$ case, you do need to do a bit more work. Your idea to show that $A_n$ has no subgroup of order 6 is correct. Well, a subgroup of order $6$ in $A_4$ is either cyclic, or isomorphic to $S_3$. Since $A_4$ has no element of order 6, we can exclude the case of a cyclic subgroup and any subgroup of $A_4$ of order 6 must be isomorphic to $S_3$.
To see that this can't happen, suppose
$$\phi:S_3\to A_4$$
is an injective homomorphism and use the fact that $S_3$ is generated by the simple transpositions $(12),(23)$. The image of these elements must be elements of order 2 in $A_4$ which are disjoint 2-cycles. Any two of these generate a subgroup of order 4 in $A_4$. Hence, no such homomorphism exists.