Cannot add certificate on Synology behind company Firewall

Another option instead of the DNS Challenge ...

Are you able to set your firewall to block everything arriving on port 80 except for requests for a specific path in the URL? More details of this are in this topic in the FAQ Peter linked: Multi-Perspective Validation & Geoblocking FAQ

If your firewall allows requests for multiple domain names you could further restrict these inbound ACME Challenge URL just for the domain for the NAS