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The Microsoft Legacy Operating System topic includes legacy versions of Microsoft operating systems prior to Windows 2000: All versions of MS-DOS and other versions developed for specific manufacturers and Windows 3/3.1, Windows 95 and Windows 98, plus any other Windows-related versions, and Windows Mobile.
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However, if the users in question use the same machines you could do it by IP address. Do you need a DNS server to resolve internal names? if not then you could assign 127.0.0.1 as the DNS server for the users machines (either manually of via a DHCP reservation). This would prevent them from accessing the internet.