That brings me to the Reimer-Tiemann reaction. This thing sucks. In my particular case, the reaction was a complete disaster. Here is a generic version of the reaction if you are not familiar with it (everyone out there except Jason).
In an effort to optimize this reaction, I consulted a recent review. Here are some of the accolades from the article.
"Even 105 years after its discovery, conditions for the Reimer-Tiemann reaction cannot said to have been optimized. This is not too surprising for a reaction in which a quantitative yield has never been reported, and in which useful yields of 3-10% are not unususal."
Nice. I guess I should have consulted this before embarking on a route invoving the "Reamed"-Tiemann reaction. Any other suggestions for the worst named reaction?
9 comments:
I remember when a certain prof here told me that I should "just do a Riemer-Tieman....you can do it in a bucket" when I went to his office for advice about a completely different matter. I went back to my desk and looked it up because I had no idea what it was. Needless to say, I quickly wrote it off as nonsense.
I'm not mistaken, that would be the same dolt who another prof recommended "just put a nitrogen in your original proposal, and he won't know what to do with it", and also disagreed with two foremost indole alkaloid chemists as to what a Bischler-Napieralski was.
You are correct in your assumption. Good times!
I've periodically wondered why people use, or even talk about, really shitty reactions that are generally known as shitty reactions. I haven't researched it, but my guess is that the reactions are either so old that they have a sort of legacy of fame (or infamy) attributed to them, or are still the best way to make something.
In other words a 5% yield sucks unless it starts with cheap materials, is easy to purify, and the alternative is multiple steps or especially expensive. A good way to make starting materials, but not a good way to make late stage compounds.
I think that maybe Prof. Dickhead might have meant you NEED to do the R-T in a bucket as opposed to implying it was a benefit. That way you might actually get some usable mass of product.
The worst named reaction is the Fischer indole synthesis. A more apt name for this transformation would be the brown intractable mixture synthesis. It is universally shitty. Plus Fischer was surrounded by crap. His Wife died very young, his first son died in WWI, his second son offed himself, and, possibly most disappointingly, his third son became a professor of (gag) biochemistry at Berkeley.
Yup, Fischer sucked so bad he only got ~17 reactions named for him and his collaborators.
Besides, the Leimgruber-Batcho does kick all sorts of ass over the Fischer indole synth.
I did not mean to denigrate Prof. Fischer merely to point out his Job-esque life.
Actually I was with you on the indole synth, until I remembered that most (if not all) naltrindole derivatives are made with the Fischer and typically have good results. Kind of odd for a well developed set of molecules with lots of functionality, but effective none the less.
2.5 years past the expiry date, here's my contribution:
http://syntheticremarks.com/?p=2084
Peace.
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