Try doing this :
grep -oP '\d+(?=/(udp|tcp))' /usr/share/nmap/nmap-services
or with perl :
perl -lne 'print $& if m!\d+(?=/(udp|tcp))!' /usr/share/nmap/nmap-services
I use a positive look ahead advanced regex, see http://www.perlmonks.org/?node_id=518444
or with awk without advanced regex :
awk '{gsub("/.*", ""); print $2}' /usr/share/nmap/nmap-services
or
awk -F'[ /\t]' '{print $2}' /usr/share/nmap/nmap-services