Most silicon transistors have a max allowed reverse-bias voltage of around 8 – 8.5V and it can be used in the same way as a Zener Diode ..
The bottom transistor adds another 0.7V as it is connected in the normal way ..
If you reverse the voltage, the story is just the opposite: the bottom transistor works as Zener”, the top transistor (normally biased) adds 0.7V ..