Wow! This sounds really bad.
First of all, your son should not be telling you anything after he does something destructive. Your son has two choices: choice 1 is to be good and choice 2 is to be bad. When he makes that second choice, he no longer gets to have any decision of what happens to him. He was bad, so now he is going to be punished. He is clearly manipulating the situation, because it is getting worse and he is starting to show his little brother that behavior like this is acceptable.
So, you need to stop this now. When your child disobeys you, whether it is not turning off the TV when you say so, or throwing a glass plate on the ground, he needs to be punished. I know that you said you tried time outs, but if you stick to them, they really work! Find a place in the room that doesn't have a lot of stuff around it and make that time out. No matter when or where he is bad, this is his time out corner.
Next time he disobeys you, he gets one warning. When he fails to comply, you tell him that he is going in time out. Put him in there for 5 minutes. I know that you have other things to do with your day besides chase around a 3 year old, but you put his little behind on that time out until he stays there for five minutes. He may get up 30 times and try to run away. You just need to keep picking him up and saying that it its time for "time out." Once he has sat through the alloted time, then he needs to discuss with you what happened. If he is trying to manipulate his way out of a punishment, then he obviously is able to understand the difference between right and wrong.
When you talk about it, ask him about what he did. Ask him why he did it. Tell him that it hurts you when he does these things. Tell him that you don't like it when he hurts your things. Make him apologize to you and then tell him you love him and let him play. He may break a rule 10 minutes later, and you have to do the same thing again. You might put him in time out 15 times in one day, but YOU MUST BE CONSISTENT! This is the only way that he is going to understand that you mean business. If you keep changing up with time outs and consequences, and positive reinforcement, then he will not know what he should really listen to. And obviously, these same rules need to apply to your two year old. He is old enough to understand!
Additionally, praise your child when he is doing the right thing. Tell him that you like the way he is playing nice with his brother. Tell him that you like how he is putting his toys away. Tell him that you like how he is eating his food with his fork. Praise what he is doing well.
But you have to stop giving him the control. He chooses to be bad, so he chooses to no longer have options. You have to be consistent with the punishments, with both children. It will work! They will learn the rules and they will follow them! I promise! It may take a week, it may take a month, but if you stick with it, it will work!