Can I suggest you save yourself a lot of hassle and install a little synchronisation program called "Allway Sync" - click here - which is very easy to set up and use.
It is free for "moderate" personal use. Just be aware that, if used excessively, it "suggests" you upgrade to the Pro (paid-for) version. If you continue to use it for more than it considers to be "moderate" use, it stops working until either you upgrade or you usage over the last 30 days drops back to their "moderate" level.
Alternatively, use Windows' Briefcase to keep files sync'd. I'm not sure what the "Synchronize" application you are trying to use is actually supposed to do, but it is based on web pages and isn't what you want to keep your data sync'd between computers.