关于when连词除了引导时间状语从句之外其它用法归纳如下：

【1】表示原因，相当于in view of the fact that; considering that；since  既然；考虑到。

How can I help them to understand when they won't listen to me？既然他们不愿听我的，我又怎么能帮助他们弄明白呢？

I can’t tell you anything when you won’t listen. 既然你不想听，我就什么也不告诉你。

【2】表示条件，when表示对某事是否会发生有把握，所表示出的这种条件其实是主句动作或意义发生的一个前提； if对某事是否会发生没有把握。

How can I get a job when I can't even read or write？如果我连读和写都不会，我怎么能找到工作呢？

How can you hope for mercy when you show none? 如果你不宽恕别人，你怎么能希望得到别人的宽恕呢？

Let you know when you need money. (I’m sure you’ll need money.)

Let you know if you need money. (Perhaps you’ll need money.)

【3】when从句中使用虚拟语气，从句表示的语气较弱，内含一定程度上的遗憾。在从句中多might, could, should等。意为“本来……却……”。

She paid when she could have entered free. 本来可以免费入场，而她却付了款。

She stopped trying when she might have succeeded next time. 她本来下次有可能获得成功，但她却不再尝试了。

Professor Li walks to work when he might ride. 李教授虽然有车可坐，但他还是步行去上班。

【4】表示对比，相当于while; whereas，意为“然而”。

They have only three copies when we need five. 他们只有三本，而我们却需要五本。

【5】强调对所描述的事件予以引人注目的强调，意为“这时；突然”。

He was still smiling when the door opened and his wife came in. 他正笑着的时候，门突然开了，他妻子走了进来。

We were about to start when it began to rain. 我们刚要出发就开始下雨了。

He was on the point of leaving when someone knocked at the door. 他刚要走就有人敲门。

黎老师列出的词典的分析也是挺合理的。

但是这里的 When 也可以理解成 considering the fact that.