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DBL%20Hendrix%20small.png College chemistry, 1983

Derek Lowe The 2002 Model

Dbl%20new%20portrait%20B%26W.png After 10 years of blogging. . .

Derek Lowe, an Arkansan by birth, got his BA from Hendrix College and his PhD in organic chemistry from Duke before spending time in Germany on a Humboldt Fellowship on his post-doc. He's worked for several major pharmaceutical companies since 1989 on drug discovery projects against schizophrenia, Alzheimer's, diabetes, osteoporosis and other diseases. To contact Derek email him directly: derekb.lowe@gmail.com Twitter: Dereklowe

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« More on the NIH's Molecular Libraries Program | Main | Yes, The Research Works Act Is Dead »

February 28, 2012

One Does Not Simply Walk Into Fluorine Chemistry

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Posted by Derek

Update: for the non-chemists in the audience who are wondering why one doesn't stroll in as advertised, check out what happens when you deal with the nastier end of fluorine chemistry. This new chemistry isn't anything like those examples - thank goodness - but it'll give you some idea of why we respect and fear the fluorine.

C&E News has an article on some of the recent fluorination methods that have been appearing in the literature. (Some of these have come up on this site here, here, and here).

These methods are all quite interesting (I've tried some of them out myself, with success), but what I also found interesting was the sociological angle that the article brought in. Organofluorine chemistry has not, over the years, been the sort of thing that one takes up lightly, for a lot of good reasons. Some of the real advances in the field have come from making it more accessible to more chemists. Very few people will use elemental fluorine other than at near-gunpoint, and some of the other classic reagents are still quite unfriendly, tending to leave cursing chemists swearing never to touch them again.

But making the field more open makes it, well, more open. And some of the people who've been there a while aren't quite sure what to make of the newcomers. They don't always cite the literature in appropriate depth, which is a real concern, and there can be a general feeling that they haven't paid their fluorine dues. (But the whole point is to keep people from paying those in the first place).

Since I'm not having to make my reputation discovering fluorination conditions, though, I'm just happy to deal with the results of all this work, both from the hardy pioneers as well as from the flashy new immigrants. These are useful reactions, and the rest of us are glad to have 'em.

Comments (24) + TrackBacks (0) | Category: Chemical News


COMMENTS

1. See Arr Oh on February 28, 2012 12:57 PM writes...

Nice tagline to this post, btw : )

"One does not simply walk into the chemblogosphere"

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2. David P on February 28, 2012 1:27 PM writes...

Good headline but where is the picture of Boromir?

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3. See Arr Oh on February 28, 2012 2:19 PM writes...

@David P - One does not simply copy pictures of Boromir...

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4. opsomath on February 28, 2012 2:21 PM writes...

"These are useful reactions, and the rest of us are glad to have 'em."

Just as glad as this non-fluorine chemist is to have his fingers.

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5. daen on February 28, 2012 2:24 PM writes...

I'll just leave this here ...

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6. Michael Goode on February 28, 2012 3:08 PM writes...

http://www.quickmeme.com/meme/36d0sj/

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7. metaphysician on February 28, 2012 5:29 PM writes...

I would think the problem is more with walking back out again intact. . .

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8. John on February 28, 2012 9:35 PM writes...

Too bad living creatures get along so poorly with fluorinated compounds. It's been quite humorous watching EPA/HHS try to walk back water fluoridation after 60 years..

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9. Shazbor on February 29, 2012 3:36 AM writes...

You can't see me, but I'm rolling my eyes.

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10. pip on February 29, 2012 5:36 AM writes...

On a more serious note, I found it disappointing that the article focuses heavily on US contributors (with a nod to China and Japan) and ignores work by people like Veronique Gouverneur at Oxford who have spent several years working on interesting and innovative uses of Fluorine, both for incorporating into molecules and controlling other chemistry.

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11. fools on February 29, 2012 7:26 AM writes...

the comments from 'established fluorine chemists' are laughable. They have clearly become confused about what they are supposed to be doing. They are working in a field, trying to discover new knowledge (presumably). Some other people come along and discover some interesting and exciting knowledge in the same area. Great. Awesome. But... "Um, actually, hang on a minute. Some of them aren't attaching my name to a tiny number buried deep in the text of their paper. WAIT! THIS IS IMPORTANT!"

If this is your biggest concern when new people enter your field and start finding out cool stuff, then you're a loser and, unfortunately, so is science for letting you be a scientist.

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12. Resan on February 29, 2012 8:39 AM writes...

Generally the comments are true, but there are several safe fluorinating agents - like MEC reagents from Daikin and Selectfluor from Air Products, which are often neglected. True these do tend to be rather expense, too expensive for most bulk application but they are very useful on lab scale to identify target molecules. When you discover a viable molecule somebody will find a way to scale it up.

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13. Resan on February 29, 2012 8:40 AM writes...

Generally the comments are true, but there are several safe fluorinating agents - like MEC reagents from Daikin and Selectfluor from Air Products, which are often neglected. True these do tend to be rather expense, too expensive for most bulk application but they are very useful on lab scale to identify target molecules. When you discover a viable molecule somebody will find a way to scale it up.

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14. Anonymous on February 29, 2012 8:41 AM writes...

fools - I had the same thought when I read that. No excitement over the new things people were doing, only "Wait, why aren't you giving ME more credit?!?!"

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15. barry on February 29, 2012 9:38 AM writes...

In the realm of fluorinations that actual med. chemists actually use, I should mention the Olah modification of the Schiemann. HF/Pyridine needs to be treated with respect as a corrosive but by not isolating the diazonium intermediate, Olah has made the process useful. A stainless Parr bomb and a plastic pipet doesn't scare chemists the way gaseous
F2 or isolating diazonium salts do.

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16. midwestern on February 29, 2012 10:36 AM writes...

When I was in grad school we developed a reaction to make aliphatic C-F bonds via nucleophilic displacement of aliphatic C-Br bonds. We used low mM solutions of HF in water/acetone mixtures with silver oxide as the transfer agent. Worked like a Finklestein reaction, with silver bromide crashing out of solution. We were developing it for radiochemical applications, hence using very dilute HF. It worked pretty well and very fast. We patented but didn't publish. Always thought it could be modified for regular synthetic applications but never looked into it. Never saw the eliminated product with secondary halides which made it very attractive to alternative methods.

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17. Hap on February 29, 2012 5:03 PM writes...

8: The problem isn't the products, but that there aren't going to be a whole lot of living things compatible with exposure to fluorinating agents. Compounds that oxidize oxygen aren't likely to be compatible with much in the way of life, including even Crichton's crystals in The Andromeda Strain.

With lack of citations - while it's probably grumpy old people wanting their credit, fluorine chemistry might be like explosives where it seems like a good idea to know how people have handled the chemistry before you came along. Fluorine chemistry is probably not helped by the closed-casket funerals of fluorine chemists or students.

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18. cyclowhat on February 29, 2012 6:35 PM writes...

@10 - glad someone made that point, Gouverneur's group especially have done some really impressive work. I kept scrolling through the article and wondering how long it would be before there was a quote from her... but nothing.
Insofar as "moaning" about lack of referencing is concerned - I think it's an entirely valid point: being able to compare the works of established F-chem methodology and the newer techniques in the field is important. If this renaissance of organofluorine chemistry is attracting wider attention, then the F-chem virgins who are reading such papers need a little context.

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19. MCPB on March 5, 2012 6:10 PM writes...

Fluorine, the one substance that really caught my attention in lab when the Professor noted he had the pliers ready to pull off fingernails if necessary.

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20. Bob on March 5, 2012 8:16 PM writes...

A college chemistry professor I once had discovered that under the right conditions that certain compounds of Fluorine are explosive. Unfortunately, he was the first to find out. He was missing his most of his left arm, and needed a new watch.

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21. Rorona on March 5, 2012 9:18 PM writes...

This is why I prefer alchemy.

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22. Ernie G on March 5, 2012 9:37 PM writes...

Back in the '70s, I worked in a research lab at a Florida phosphate company, trying to find an economical route from fluosilicic acid (H2SiF6), which was cheap, and which we had plenty, to the more valuable HF. We had a textbook, Toxic Properties of Inorganic Fluorides, by Eagers. Everyone on the project was required to read the chapter with clinical descriptions of the last hours of people who had inhaled even a few drops of HF. That put the fear of God in them. Based on recommendations in Eagers' book, we had the ER at the local hospital prepare an HF tray, just in case. They never had to use it.

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23. Ernie G on March 5, 2012 9:38 PM writes...

Back in the '70s, I worked in a research lab at a Florida phosphate company, trying to find an economical route from fluosilicic acid (H2SiF6), which was cheap, and which we had plenty, to the more valuable HF. We had a textbook, Toxic Properties of Inorganic Fluorides, by Eagers. Everyone on the project was required to read the chapter with clinical descriptions of the last hours of people who had inhaled even a few drops of HF. That put the fear of God in them. Based on recommendations in Eagers' book, we had the ER at the local hospital prepare an HF tray, just in case. They never had to use it.

Permalink to Comment

24. linus paulring on March 5, 2012 11:56 PM writes...

It would probably also help if you explained the LOTR reference to non-chemists.

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