Because "/" was already used as the command switch character in DOS 1.X which didn't yet have folders ((boggle)).
Source traced back to DEC TOPS-10, which MS founders were exposed to. Then a conservative manager (piece blames IBM) chose backwards compatibility over consistency with Unix, thereby dooming billions of regular folks to need an explanation what a backslash is compared to a slash.
"compatibility with unix" didn't matter in those days.
There were many, many OS's, all running on computers so expensive (for whichever micro/mini/mainframe segment) that most people didn't expect to replace them, ever.
cpm
vms
tops10
tops20
unix
multics
rsx11
mvs
os/360
gcos
apple dos
etc etc etc.
I know we all love bagging on Microsoft, but insisting on backwards compatibility with the system you're directly replacing is not an unreasonable decision, especially since changing it could well have made DOS 1.1 scripts silently destroy data when run in DOS 2.0.
Source traced back to DEC TOPS-10, which MS founders were exposed to. Then a conservative manager (piece blames IBM) chose backwards compatibility over consistency with Unix, thereby dooming billions of regular folks to need an explanation what a backslash is compared to a slash.