I'v add path to windows path variable:
path="C:\Program Files (x86)\CodeBlocks\MinGW";"C:\Program Files (x86)\CodeBlocks\MinGW\bin";%path%
then in my work directory, star a command window, run:
mingw32-gcc -o app main.c
mingw32-gcc: error: CreateProcess: No such file or directory
If I compile using the code::blocks IDE, the project is compiled ok.