When you have multiple accounts and an IMAP account in Outlook 2010/2013 and you change the default sending account to the IMAP account, you may experience the following issues:
Out of the box, Outlook 2010 SP1 and Outlook 2013 use the default account for Send to commands but not for new messages created while viewing a pst file (when a POP account is assigned to the pst file), unless you set a registry value to always force the use of the default account.
To force all new messages to use the default email account, regardless of which pst file you are viewing, browse to the following registry subkey in Outlook 2010 and add a DWORD named NewItemsUseDefaultSendingAccount:
HKEY_CURRENT_USER\Software\Microsoft\Office\14.0\Outlook\Options\Mail
DWORD value: NewItemsUseDefaultSendingAccount
Value: 1
In Outlook 2013, the key is:
HKEY_CURRENT_USER\Software\Microsoft\Office\15.0\Outlook\Options\Mail
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