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This failure could be caused by several things.
It would be helpful to (enable SSH login if needed and) do some very basic tests right from that system.
Actually, I'm not sure that the Synology ACME client requires HTTP authentication.
I think you may need to review the Synology help site for troubleshooting details.
I am trying to do that now - but I my mojo for networking is weak.
odd thing is I successfully did create certs before but stupidly deleted before backing up.
The Synology is connected to a Orbi Satellite, I will plug directly into the FIOS Router and reboot. Right now, i do not see it's IP listed in the FIOS Router so taking out the Orbi might be smart to do
I am on FIOS if that matters. I will peek trying to configure to forward pots.
I am able to create a new cert - thanks for all the help and patience. I enabled DDNS and it asked me to generate a Let's Encrypt Cert and that succeeded. I can now create new certs through the Certificate path.