Hi
prindte,
If you have users still using the old @b.domain.com as EmailDomain.
You might want to add the relevant DNS entries in the DNS servers, if not present.
Configure an accepted domain within your Exchange organization as authoritative:
https://technet.microsoft.com/en-us/library/jj657734(v=exchg.150).aspx
Before you configure an accepted domain, you must verify that a public Domain Name System (DNS) MX resource record for that SMTP namespace exists and that the MX resource record references a server name and an IP address associated with your Exchange organization.
Also the autodiscover.b.domain.com need to be pointing to the correct server.
If you want to totally decommision the domain, then make sure you remove the domain from accepted domain in Exchange, and then remove them from all the users and later remove the DNS entries.
However doing so might give rise to NDRs when users in outlook tries to reply to old emails containing old domain addresses. Also sometimes due to cached contacts it would generate ndr. And there is no automated solution for users outside your organization
replying to old emails.
Best would be keeping @b.domain.com as secondary and make @a.domain.com Primary for each user ac