With you saying that you have the CD version of the game, I take it that it's patched up to v1.9, yes?
Also, it sounds like the launcher is failing to hook your game due to insufficient privileges. I suggest setting both your game and cnconline.exe to always run as administrator by going to their Properties > Compatibility > Checking the box for Always run as Admin.
After setting the new settings to the exe's, launch C&C:Online's launcher, unhook your game, re-hook it, then close the launcher completely. After that, launch Tiberium Wars directly from CNC3.exe or the shortcut you have for it--the launcher should pop up and you will need to press the CNC3 button.
That should fix the issue; you may also try reinstalling the C&C:Online launcher to ensure that the registry keys it sets are added correctly (that sometimes tends to be an issue for some people).
Let us know if the above works for you or not; if it hooks correctly, the game should not freeze once you select the multiplayer button. If a different error occurs when logging in, then that is a different issue (i.e. general connectivity) that can also be solved.