Issue Date: July 10, 2017
Synthesis of lysergic acid
The first total synthesis of lysergic acid was reported some 60 years ago by six chemists at Lilly Research Laboratories and R. B. Woodward of Harvard (J. Am. Chem. Soc. 1956, DOI: 10.1021/ja01594a039). This historic achievement has been called “Woodward’s synthesis of lysergic acid” ever since, which I contend is a misnomer. In the recent Woodward centenary article (C&EN, April 10), the illustration on page 31 perpetuates the error by presenting this as the work of “Woodward’s group,” which it isn’t.
The JACS paper sets out with Woodwardian flair to trace a path from early lore to the key “artifice” of using dihydroindoles as intermediates. What follows is a tortuous saga of dead ends and ingenious detours. Surely, while some of these sprang from Woodward’s imagination, others were born of the mastery of seasoned process chemists. Sorting these out appears futile and is arguably pointless. From the travail arose the successful route, conveyed briefly in the preliminary communication and disclosed at length in US Patent No. 2796419. In the patent, inventorship—the legal standard of intellectual input—is accorded to Lilly chemists Kornfeld, Kline, and Fornefeld. So to be fair, let’s call this classic endeavor “the Lilly-Woodward synthesis of lysergic acid” to recognize the great maestro and his industrial colleagues alike.
I was interested in the Newscripts of April 3, 2017 (page 56), regarding the stamp collection of Maurice Snook. Of his 250 or so such stamps, C&EN chose to show one of Gerty Cori. Well deserved. I was responsible for the background design of glucose-1-phosphate (the Cori ester) shown on the stamp. When the image of the stamp was first published in C&EN several years ago (Dec. 17, 2007, page 29), I and some astute readers immediately noticed that the structure was incorrect (Jan. 28, 2008, page 104). I need to explain that. When the U.S. Postal Service was to make the final version of the stamp, someone decided that the phosphate group was too close to Dr. Cori’s chin. So they moved it over. But they didn’t adjust the C–O bond! Nor did they tell me what they had done. I suppose we should not expect the Postal Service to have scientists around. To their credit, however, they have produced a wonderful series of stamps that honor scientists.
Carl Frieden, St. Louis
I would like to comment on the interview with Dr. David T. Hobbs which was carried in the May 15 issue of C&EN (page 26). The unexplained rupture of a drum of nuclear waste was discussed which occurred at the Waste Isolation Pilot Plant near Carlsbad, N.M. The cause of the rupture and release of radioactive material was proposed to be due to a cat litter organic sorbent reacting with oxidizing (nitrate) waste. What is unexplained is why only one drum out of nearly 700 gave this activity. Other drums were not affected.
Organic cat litter could react as proposed and probably did. It is proposed that an inorganic sorbent such as a zeolite would have been the safe way to go. However, the original specification was for kitty litter/zeolite clay.
With the above information on hand, I would like to make known an incident using zeolites in the drying of oil. The zeolite was regenerated by passing hot air over the used (wet) sorbent, which resulted in a fire. Later tests showed the zeolite lowered the ignition temperature of the oil, which was on the surface of the zeolite. One concludes that zeolites can act as a catalyst. Could some zeolite have been in the drum that ruptured? Do zeolites catalyze reactions as in the drum considered? More testing is needed.
Clarence G. Johnson Jr., Memphis
Microbiome in cosmetics
This letter is concerning the cover story of the print copy of the May 8, 2017, issue (page 30) of C&EN titled “The microbiome comes to cosmetics.” In a nutshell, the article described the inclusion of microbials in cosmetics materials to be smeared on human skin. Going with that theme, the article is decorated with several cartoon images of various types of microbials. I am writing about the cute green cartoon of a microbial structure shown on the center right-hand side of page 32. I’m no microbiologist, but this cartoon looks very similar to electron micrographs of the famous shepherd’s crook structure of the filovirus family, which includes the Ebola and Marburg viruses. These are not the type of biological additives that would improve skin health! Let’s hope that the cosmetics companies mentioned in this article are paying more attention than C&EN as to what they put in their products!
Jason J. Reddick, Greensboro, N.C.
Re: The secret to great wine? Organic chemistry.
A reader’s question about this June 12 article received responses from two coauthors of the book mentioned in the article. (cenm.ag/winechemistry)
As an organic chemistry professor/winemaker for nearly 40 years I look forward to Professor Waterhouse’s book. I have a question regarding wine in contact with synthetic corks. Will taste and aroma be affected? My favorite wine compound is 2-isobutyl-3-methoxypyrazine.
Gordon W. Gribble
Hi Gordon, I hope you enjoy the book. Corks (especially synthetic) can scalp aromas from wine. Clean corks can even adsorb compounds from within wine that are associated with cork taint (haloanisoles). Your favourite compound is one of the most potent odorants in wine. When we work with it in the lab it can stink the whole building out if we’re not careful!
Synthetic corks do not have the taint problem of natural corks (trichloroanisole) but both natural and synthetic do adsorb some non-polar substances that have aroma potential. In general they impart very little to the wine. Some tasters refer to a slight (normal) cork aroma. There is negligible effect on actual taste, [e.g.,] sweet, sour, bitter by closures.
Re: Engineered microbes make ‘natural’ colorants
A reader noted the potential advantage of synthetic over biosynthetic approaches. (cenm.ag/engmicrobes)
The challenge with these fully biosynthetic approaches is that if one looks at full life cycle analyses they are often both less green and more expensive than fully synthetic or semi-synthetic approaches. Genencor about 15 years ago metabolically engineered a system to produce Indigo. It was technically successful but failed in the market for cost reasons. Also, their life cycle green analysis showed that the bio-indigo was less green than the synthetic version.
Allen Hunter via Facebook
Re: What’s in fireworks, and what produces those colorful explosions?
Readers shared thoughts on these celebratory explosions online. (cenm.ag/fireworks)
So very interesting so please enjoy a blast from the past.
When developing an environmental programme for the Sydney Olympic Games, it came to our notice that as well as the potential for dioxins in the huge landfills [carefully remediated], there was also the potential for dioxin to be emitted by fireworks displays around the opening and closing events at these, the second “green” Olympics ... the first were in Lillehammer.
Anyway, the source of the potential emissions was the PVC tape that was used [as] part of the design and set up the fireworks. It was a genuine issue which the organisers took seriously, if only to safeguard much prized environmental credentials. I understand that a substitute for the PVC was found. These days, 15 years on, I continue to think about what we learnt from this situation and whether the knowledge was adopted by the fireworks industries in other places. I don’t know if they maintained this improved practice even here in Sydney where the issue was first address[ed].
I notice the complete omission of the metal lead. Yet this is so often in fireworks as the initiators of the reactions in the forms of styphnate and lead peroxide.
I also work for IATSE USA829 and we have been pretty successful in getting the lead pyro bullet hits replaced with the lead-free alternatives in film industry shoots here. It would be nice if the pyrotechnics could do the same.
Here are excerpts of a Facebook Live chat, in which readers asked questions online, and C&EN staff answered in real time on video. View the entire chat at cenm.ag/cenvideos.
What do you find most rewarding about science communication?
The engagement with our readers is really rewarding. We write for really educated people who are doing work that is shaping the world around us.
Matt Davenport, associate editor
One of the most rewarding things is telling stories about chemists. Chemists are such interesting people, and they have so many different facets of their lives.
Linda Wang, senior editor
How do you find ideas for a story?
As you start reporting stories, you always learn details that never make it [into the final story], and some of those details turn out to be the nugget of your next story. You’re always learning, and each thing you learn is an opportunity for a new story.
Matt Davenport, associate editor
There are so many stories out there, and it’s just a matter of [uncovering them].
Linda Wang, senior editor
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