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I'd like to restrict SMTP login for certain users to my Exchange 2010 servers. I've been looking at the receive connectors, but I can't find a way to remove the "Exchange Users" role from specific accounts. Anyone know of a way to do this?

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Why are you wanting to do this? What are you trying to accomplish?

If you are wanting to prevent them from sending but still allow receiving you can just crank down their send limit.

In the mailbox properties, Mailbox Settings, Storage Quotas.

Uncheck the "use mailbox database defaults"

Set the "Prohibit Send" to something like 1MB.

That will prevent them from sending out email but they'll still be able to receive.

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The issue we're having is with users responding to phishing attacks and the subsequent intra-organization spamming. The accounts in question are all mail contacts with cloud-based email. I can't get approval to limit SMTP to our hosted mail filter's IPs, so I wanted to remove the ability to connect to SMTP for these mail contacts so I can cut down on the number of accounts that could possibly be compromised. –  Paul Dec 17 '12 at 17:50
    
So you are wanting to limit their SMTP access to your Exchange server or to their own SMTP server on the internet? If it is the second, then you'll need to know what that SMTP server is and just deny outbound SMTP on your firewall to those servers. –  TheCleaner Dec 17 '12 at 19:16
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