does the cpu fan ramp up to max when under load? (e.g. read with cpuid hwmonitor or other software that you might use...)
do you have any profiles for fans that are delaying the spin ramp-up?
the instant increase to 80 is somehow normal (instant means 1-2 seconds right) but i suspect that it does not remain there and will continue to increase to 90 Celsius.
from my understanding (not an owner of 212) you might get around 75 Celsius average (give or take depending on your luck - every 4790k is different)
also when stock, do you apply stock voltages? check this aspect as you might have increased the voltages unnecessarily...
regarding OC - i would refrain to apply 4.6ghz till you find way to reduce temps. 100 is too much.
reapplied thermal paste - did you use some cleaning kit? make sure no fingerprints or residue remains, use microfiber for final cleaning before applying the thermal paste. also i assume that you applied right quantity - i guess center blob is the most accepted method for haswell.
in general 212 will not give you plenty of room for overclocking that CPU. it's too small, half of high end air coolers, which are also limited for OC, depending on the CPU model.