Current TinyMCE release has two style sheets associated with TinyMCE. one is to format the editor appearance. The other is to allow the content window to match the css that is use in the site; this is to give visual feedback to the one using TinyMCE; so if you have css for the site that indents the first line of a paragraph; TinyMCE will show paragraphs in the editor with the first line indented. This is the content.css. This can be set through the init: content_css : "css/custom_content.css",
The styles drop down list is suppose to be populated in the TinyMCE init; this is stated in the documentation and can be found on the website.
Example of usage of the style_formats option:
tinyMCE.init({
...
style_formats : [
{title : 'Bold text', inline : 'b'},
{title : 'Red text', inline : 'span', styles : {color : '#ff0000'}},
{title : 'Red header', block : 'h1', styles : {color : '#ff0000'}},
{title : 'Example 1', inline : 'span', classes : 'example1'},
{title : 'Example 2', inline : 'span', classes : 'example2'},
{title : 'Table styles'},
{title : 'Table row 1', selector : 'tr', classes : 'tablerow1'}
]
});