No, the compiler is absolutely not allowed to optimize those two writes into a single double word write. It’s kind of hard to quote the standard since the part regarding optimizations and side effects is so fuzzily written. The relevant parts are found in C17 5.1.2.3:
The semantic descriptions in this International Standard describe the behavior of an
abstract machine in which issues of optimization are irrelevant.
Accessing a volatile object, modifying an object, modifying a file, or calling a function that does any of those operations are all side effects, which are changes in the state of the execution environment.
In the abstract machine, all expressions are evaluated as specified by the semantics. An actual implementation need not evaluate part of an expression if it can deduce that its value is not used and that no needed side effects are produced (including any caused by calling a function or accessing a volatile object).
Accesses to volatile objects are evaluated strictly according to the rules of the abstract machine.
When you access part of a struct, that in itself is a side-effect, which may have consequences that the compiler can’t determine. Suppose for example that your struct is a hardware register map and those registers need to be written in a certain order. Like for example some microcontroller documentation could be along the lines of: “reg0 enables the hardware peripheral and must be written to before you can configure the details in reg1”.
A compiler that would merge the volatile object writes into a single one would be non-conforming and plain broken.