[cratylus]

Hello! I have an experiment set up and I would greatly appreciate it if someone could double check my logic here or offer any advice.

The idea is to alkylate naphthalene with chloroacetone slowly generated from a solution of CuCl2 in acetone, at RT. Because the chlorine is released very slowly, naphthalene should be in excess for now.

Is the CuCl2 a good enough catalyst for the Friedel Crafts, or is something else needed? A fine grey precipitation of CuCl is also slowly produced, might that itself catalyze the reaction?

And what proportion of 1 and 2 monosubstitution and/or multi-substitution does theory predict? I read that disubstitution is not greatly favored, but often seems to be because the stuff stays in the vicinity of the catalyst. Unless the CuCl enters into it, that shouldn't be the case right?

Thank you!

[opsomath]

This is a very interesting reaction that I haven't encountered before. Do you have a reference for it that I can look at?

[cratylus]

You've never heard of the Friedel Crafts alkylation! My, my... :p  Zinc chloride, aluminum chloride, iron chloride, all sorts of things work, but there are few references to cupric chloride. But that might just mean it's less efficient. Cu-catalyzed FC there's a reference here or there I can't access. This might be interesting. http://pubs.rsc.org/en/Content/ArticleLanding/2010/CC/C0CC02584D

I was kinda hoping y'all would be more knowledgeable on that subject.

Where I heard of chloroacetone made this way was in a paper that mentioned somebody "observed that solutions of copper chloride in acetone gradually lost their color" or something. Here's one: http://pubs.acs.org/doi/abs/10.1021/ja01625a016

It is apparently known to a-chlorinate carbonyl substances, as well as effect aromatic halogenation. In this case I'm not sure which will win out but that's to be determined.

So I figured if copper chloride is also a suitable lewis acid, then I might have a nifty system to experiment with.

[opsomath]

Hey, you know that Chem Comm paper has their procedures in the SI, which anyone can access.

http://www.rsc.org/suppdata/cc/c0/c0cc02584d/c0cc02584d.pdf

It's a weird reaction though, apparently using an imidazole-Cu complex as a leaving group!