tl;dr  Edit /usr/syno/etc/synoservice.d/httpd-user.cfg to look like: 
   {
        "init_job_map":{"upstart":["httpd-user"]},
        "user_controllable":"no",
        "mtu_sensitive":"yes",
        "auto_start":"no"
    }
Then edit the stop on runlevel to be [0123456] in /etc/init/httpd-user.conf:
Syno-Server> cat /etc/init/httpd-user.conf 
description "start httpd-user daemon"
author "Development Infrastructure Team"
console log
reload signal SIGUSR1
start on syno.share.ready and syno.network.ready
stop on runlevel [0123456]
...
... then reboot.
Background infrormation
The answer given by Backslash36 is not the easiest solution and it may also be more difficult to maintain.  Here, I give a solution that also doesn't involve starting webstation, which most other solutions demand.  Note, for updated documentation see here, which gives a lot of info in general about the synology systems.
It is important to note that the new DSM (> 5.x) use upstart now, so much of the previous documentation is not correct.  There are two httpd jobs which run by default on the synology machines:
httpd-sys : serves the administration page(s) and is located on 5000/5001 by default. 
httpd-user : this, somewhat confusingly, always runs even if the webstation program is not enabled.   
If webstation:
- is enabled: then this program serves the user webpages.
 
- is not enabled: then this program sets 
/usr/syno/synoman/phpsrc/web as its DocumentRoot (/usr/syno/synoman/phpsrc/web/index.cgi -> /usr/syno/synoman/webman/index.cgi), meaning that a call to http://address.of.my.dsm will call the index.cgi file.  This cgi file is what drives the redirect to 5000 (or whatever you have set the admin_port to be). 
From the command line, you can check what the [secure_]admin_port is set to:
Syno-Server> get_key_value /etc/synoinfo.conf admin_port
5184
Syno-Server> get_key_value /etc/synoinfo.conf secure_admin_port
5185
where I have set mine differently.
Ok, now to the solution.  The best solution is simply to stop the httpd-user daemon from starting.  This is presumably what you want anyways (e.g. to start another server like `nginx' in a docker).  To do this, edit the relevant upstart configuration file:
Syno-Server> cat /usr/syno/etc/synoservice.d/httpd-user.cfg 
{
        "init_job_map":{"upstart":["httpd-user"]},
        "user_controllable":"no",
        "mtu_sensitive":"yes",
        "auto_start":"no"
}
so that the "auto_start" entry is "no" (as it is above).  It will presumably be "yes" on your machine and by default.  Then edit the stop on runlevel to be [0123456] in /etc/init/httpd-user.conf:
Syno-Server> cat /etc/init/httpd-user.conf 
description "start httpd-user daemon"
author "Development Infrastructure Team"
console log
reload signal SIGUSR1
start on syno.share.ready and syno.network.ready
stop on runlevel [0123456]
...
This last step is to ensure that the httpd-user service does actually start, but then automatically stops.  This is because there are otherwise a number of services that depend upon it actually starting.  Reboot your machine and you will now see that nothing is listening (or forwarding) on Port 80.