http://ftp.fr.debian.org/debian/tools/md5sum-w32.zip

This utility computes MD5 checksums of files, ignoring end-of-line
conventions unless the -b (binary) flag is set. 

usage: md5sum [-bv] [-c [file]] | [file...]
Generates or checks MD5 Message Digests
    -c  check message digests (default is generate)
    -v  verbose, print file names when checking
    -b  read files in binary mode
The input for -c should be the list of message digests and file names
that is printed on stdout by this program when it generates digests.

So, if you want to generate a MD5 sum for a certian file cdimage.iso,
open a command console (Start/Run and enter "command"), and issue the
command "md5sum -b cdimage.iso".