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We had the same issue after converting from 6i to 10g. Sometimes 10g is blocking a SYNCHRONIZE in a WHEN-VALIDATE-ITEM as restricted. Forms 10g is wrong as SYNCHRONIZE is not (and has never been) a restricted built-in.
I could never make it into a simple reproducable testcase to show to Oracle. In our case we could safely remove the SYNCHRONIZE built-ins from the code. Most of the times they were added in the past to workaround bugs in Forms 4.5 or 5.x.
On MetaLink you can find a couple of bugs in Oracle Applications running into the same issue and they were also resolved by removing the call to SYNCHRONIZE. I also find bug 1577072 (open since 2001)
If you need further assistance you'll probably have to log an iTAR at http://metalink.oracle.com