nav ul:first-child li a {
color:red;
}
nav ul:first-of-type li a {
color:red;
}
nav + u li a {
color:red;
}
<nav>
<ul>
<li><a href="#">link 1</a></li>
<li><a href="#">link 2</a></li>
<li><a href="#">link 3</a>
<ul>
<li><a href="#">sub link 1</a></li>
<li><a href="#">sub link 2</a></li>
</ul>
</li>
</ul>
</nav>
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