The University of Cambridge has a site with a collection of interesting and possibly even useful Applets for chemical calculations. It has a graphic feature for help in visualizing relationships. Of particular interest is the Rotovap Simulator Applet.
Ruthenium remains at US$490/toz in the EIB.
While tunneling deep through the compacted patent strata, I happened to notice that E. J. Corey’s oxazaborolidine patent appears to be expired. US Patent 4,943,635 (July 24, 1990) was assigned to the President and Fellows of Harvard College and listed Professor Elias J. Corey as inventor. This is a patent with 30 claims, of which 3 are independent claims. All of the claims are for composition of matter.
The description teaches methods of preparation of a variety of oxazaborolidines, with a special emphasis on the preferred embodiment based on proline. The use of the catalyst for asymmetric reductions is taught in the description as well.
Curiously, Corey is the only inventor on the patent. Hmmm. Knowing that he was well into his career by 1988 when the application was filed, I can only guess that he must have been very busy running multiple reactions, doing flash columns, and burning NMR spectra. \;-)
The next oxazaborolidine patent to expire will be the Merck US 5,039,802 (Aug. 13, 1991) patent. This is a process patent claiming a method for the preparation of the diarylproline system using aryl Grignard addition to a pyrrolo[1,2-c]oxazole-1,3-dione.
Incidentally, I did witness a famous professor actually doing bench chemistry. A friend and I were wandering around the chemistry building at her alma mater, (The) Ohio State University, in March of 1993 when we happened past the lab of Mel Newman.
There he was, in his 90’s, intently shaking a 2-liter separatory funnel of some dark hellbroth. He was isolating a polyaromatic hydrocarbon that he made. Newman graciously stopped to talk about his work. Having freshly graduated from a stereochemistry group and a stereochemistry post-doc, I nearly fainted when I met him. It was like meeting Elvis. Newman passed away a few weeks later.
Our local area is graced with the presence of a biomedical drug production facility. The company manufactures important, lifesaving products from which mankind benefits and in doing so, the company makes a handsome profit. They also have a production facility in a Caribbean Island Territory which also manufactures important products. I understand that they are a very progressive organization. Friends, family, and colleagues from grad school work at the local plant and at the R&D office in Many Trees, in some coastal state. [Note: the name and location have been cleverly disguised or omitted- Th’ Gaussling]
Meanwhile, there is a constant buzz concerning the possibility of moving the entire mfg operation to this Caribbean paradise where the tax and labor costs are significantly lower. I have no special inside information here, I just know that this has been considered.
The situation outline is in no way unique to the particular company I’m thinking of. It is a very common situation. Company decides to move operations off-shore to continue profit growth of a successful product. Shareholders continue to enjoy good returns on their investment, product pricing is competitive and the company continues to hold on to market share. Everybody’s happy, right?
Back at the corporate HQ, assets are safely nestled in the Unites States of America, under the 24/7 protection of the Army, Navy, Air Force, Marines, and Coast Guard. Corporate human and capital assets (shareholder assets, really) enjoy the benefits of the vast infrastructure of the USA. Materials and people move safely and efficiently over land and through the skys of the USA. The FAA assures air safety and orderly movement in the skies. The DOT assures motor vehicle safety. State and federal monies provide for highways, bridges, and all of the motorway infrastructure to keep the trucks of raw materials and product moving.
Federal, state, and local governmental agencies provide reservoirs for water and electricity. Plant process water comes from a pipe put in place by the local water district infrastructure. Sanitary water treatment is provided by the municipality. The streets are patrolled by city and county police who are charged with crime prevention.
Corporate scientists who invent the technology that the company profits from so handsomely and the executives who guide product to market were educated within the vast academic/research complex that has made the USA the envy of the world. Graduate student and post-doctoral stipends in science and engineering are largely funded by some government agency or other.
Corporate researchers have access to enormous volumes of public domain technology and knowledge paid for by NSF and NIH grants. Researchers who were educated at public institutions with public subsidies take their talent and generate treasure for the corporations and the shareholders.
Yet, a great many corporate entities are escaping tax liability by moving manufacturing off-shore. Corporations whose very existance is owed to their fertile, wealthy, and knowledge rich nation have somehow seen fit to evade paying back into the system so as to perpetuate that very system from which they benefit so handsomely. Instead, others contribute to sustain it.
The advantage of substantial US infrastructure amounts to a kind of subsidy. The purpose of this subsidy is to stimulate the formation of wealth generating organizations who can then provide jobs and stability for the economy. Instead, we find that corporations are tapping US knowledge wealth and eventually using it to subsidize foreign economies.
There are mathematical justifications for this transfer of manufacturing from the local to the foreign. More profits flow to the shareholders- the big players and those who hold 401(k) plans. Growth is sustained and a competitive edge is held. But is it really? Could it be just the result of poor imagination?
On page 14 of the July 30, 2007, issue of C&EN, an article entitled “Bill Mandates Public Access” by David Hanson describes a section of a bill recently passed from the House to the Senate. The relevent text from the bill is as follows-
SEC. 217. The Director of the National Institutes of Health shall require that all investigators funded by the NIH submit or have submitted for them to the National Library of Medicine’s PubMed Central an electronic version of their final, peer-reviewed manuscripts upon acceptance for publication, to be made publicly available no later than 12 months after the official date of publication: Provided, That the NIH shall implement the public access policy in a manner consistent with copyright law.
Hanson’s article states that the Professional and Scholarly Publishing (PSP) Division of the Association of American Publishers has asked members of Congress to reconsider this bill, or at least the mandatory submission to PubMed. Hanson reports that the PSP claims that-
“This language could serve to undermine the existing system of peer review and scholarly publication which disseminates high-quality research findings throughout the scientific community,” …
Further down, Hanson gets to the real issue-
Brian D. Crawford, chair of the PSP committee and senior vice president of the Journals Publishing Group at the American Chemical Society (which publishes C&EN), says the House language violates fundamental copyright principles. The bill “would essentially force authors and publishers to, in essence, forfeit their copyrights” without compensation for their investments and would have many negative impacts on private-sector publishers, he says. [Italics by Gaussling]
What is telling is the quote by Brian D. Crawford, who suggests that the publishers stand to lose their copyright on the copy submitted by the NIH funded researchers. If you are a publisher, should you be worried about this? Probably. The gravy train may be leaving the station.
Yes, the publishers have invested large sums in building publishing and distribution systems for the profitable dissemination of information. But I would add that they have built these publishing engines on a system that hands voluminous copy to them for free. Unlike other publishers who have to pay their authors for content, academic publishers do not pay contributors who, I might add, provide some incredibly valuable content. Academic publishers have built publishing businesses using content paid for by government granting agencies, and by extension, the public.
It’s easy to fault publishers for taking advantage of a system that hands them publishable content for free. But, on the other hand, circulation numbers for most publications is quite modest. Even if advertising is used, the typical low circulation of any given specialized scientific journal is so low that only very modest advertising rates could be obtained. Many journals survive on subscription fees alone. Examples of journals that have come to terms with advertising are J. Chem. Ed., Nature, and Science.
The scientific publishing system is a sort of a deal with the Devil- the scientist gets the grant, does the work, and then what? After dinner talks at the Elks Club? Of course not. A manuscript is prepared and in exchange for free printing and distribution, the publisher obtains the copyright. The copyright is the key. It is a cash cow in the same way that the copyright to the Beatles songs are a cash cow, only with smaller numbers.
I think that Sec. 217 of H.R. 3043 is the right idea. The public has already paid for the research. Why should it be intercepted at no cost by printers who then have an everlasting copyright and control of what is rightly national treasure? The citizens have to pay taxes for the research and then turn around and pay commercial interests for the right to read it. That is wrong.
If commercial interests want to make a profit on scientific publishing, then they need to find a better model. The public shouldn’t be barred from access to what they have already paid for. Advertising may be the way to do it. Perhaps the funding agency should have the copyright and publishers pay a fee to print and distribute it? Comments?
Looking for a career change in chemistry? Tired of loading other peoples samples into that GC sample carrousel? When you close your eyes do you see the pink color of phenolphthalein swirling in a flask? If so, then maybe it’s time to step up to the fabulous world of Over The Road Trucking- OTR.
I understand that drivers with a CDL and a hazardous materials endorsement can expect to find many well paying opportunities out there.
One of the fun “burdens” of blogging is the constant pressure to write new posts with new content. Since I am not Jacques-Yves Cousteau or Henry Kissinger, I have to thrash around for ideas that are compelling yet not in conflict with confidentiality issues related to my career. I have much to say about many fascinating chemistries in diverse industries that, owing to confidentiality, I’ll have to take to the grave. No doubt there are many other bloggers out there who are in the same pickle.
As I get further into this activity I am constantly impressed with the number and variety of really bright people out there writing blogs. I have tried to highlight a few of them on the Blogroll of this site. The flow of good blogs, commercial or amateur(ish), continues to accelerate.
What is disappointing about blogging is the continued growth of snarky, half-assed commentary. I have been fortunate on this blog to receive very thoughtful and insightful comments, and for that I am grateful. I have only edited out a handful of inappropriate responses. I suspect this is due to the specialized nature of this blog, modest visitation rate, and its content. The blogs with the most negative or ill conceived comments seem to be those that are visited by a broader group of participants.
As we move forward with this form of communication, it becomes apparent to me that the need for edited content is as great as ever. Take this blog for example. I could easily take the encyclopedic approach and spend all of my efforts writing pedagogical content. Even if someone liked such content, there would always be the nagging issue of credibility. Without good editors and gate keepers, factual content and editorializing would inevitably meld into a dried brick of pedagogical poundcake that no one could trust. In fact, one could not even trust that the poundcake would be the same from one day to the next.
I’m not sure how we’ll deal whith the problem of unedited content. I am alarmed at the amount of reliance on the www content that I am hearing from university friends and from public school teachers. I think we should all revisit the library for an update on what makes information credible.
A nice preparation of nitroalkenes appeared in the latest JOC. The work was reported by Concellon, et al., JOC, 2007, 72, 5421-5423.
I like the two obvious aspects of this work- catalytic use of NaI and the use of SmI2 for functional group modification. The use of 0.15 eq of sodium iodide to catalyze the condensation is really clever. The yields are reported to range from 55 % to 96 %. A few yields are in the mid 50’s range yet no mention is made of dimerization of the bromonitromethane, so I can assume that is not much of an issue.
The process uses an excess (2.5 eq) of SmI2 to afford overall 2 electron transfer to the substrate, resulting in loss of Br dot and oxygen, yielding an olefin with good stereospecificity. For the examples given, the E/Z ratios were all 98/2.
There are some downsides to the chemistry, I’ll admit. Plant management may not be keen on nitromethane derivatives. I know that nitromethane has been shown to be shock sensitive in the BOM impact test (personal communication). Depending on their threshold for these things, the plant safety patrol boys may have misgivings.
The economic merit of scaling up a process that uses SmI2 depends entirely on the value proposition, which can be readily calculated. Rare earths are reportedly of low toxicity, though I have not seen a primary reference for that assertion.
Most of the rare earth elements come from FSU or China. There is an accessible supply outside of the usual catalog companies, though you may have to do an electronic funds transfer in advance to some cramped office in Shanghai with a rep named Sylvia or Frank. Advanced payment and sketchy D&B data will make your accountants skittish. But it could be worth it for bulk material.
I’m increasingly aware of the interesting utility of more than a few of the rare earth elements. My work post-academia has taken me to many far off and exotic locations on the fabulous periodic table. The rare earth group is not the featureless corridor of nondescript trivalent cations that this organikker once believed. Fancy that.
Even the biggest pollyanna in the sales group will discover one day that it is possible to have a bad customer. Yes Johnny, it is a fact that not all customers are desirable. Oh I know, in sales one is always rabid to close the deal. Get the sale and move on to the next prospect with a pulse. But what is the difference between a good customer and a bad customer if their money spends the same?
Ideally, a “Great” customer comes back for repeat business, is flexible on terms and conditions, pays 30 days net, gives long lead times for delivery, accepts FOB terms, accepts delays and price increases without protest, and picks up the dinner tab when out for a visit. [~~Sound of needle scraping across phonograph album~~]
If only such compliant customers existed (Sigh). In reality, most chemical customers are in what I would call the “Good” category. That is, they have reasonable expectations of price and delivery as well as an understanding of what constitutes fair business practice.
But on occasion one runs into what you might call a “bad” customer. Such customers are found across the entire spectrum of size and business model.
A bad customer is one that consumes excessive resources during the course of service.
A small bad customer might want you to do free product development for them, or may try to negotiate bulk pricing only to turn around and try to get bulk pricing on small quantities. Bad customers may finagle front-run samples from you and then disappear for months or years without a peep.
Large bad customers like to throw their weight around. They know they are above you on the food chain and behave accordingly. They dangle promises of big and long term sales and wangle free services from you. Services like gratis process development, holding inventory for free, tolling or other business agreements that tie your hands and force you to open your books for their auditors.
Bad customers large and small have other maddening habits that consume resources. Specifications that change over time, always to the side of higher stringency, are a favorite of bad customers. Bad customers will discover that they can shave costs by elaborate just-in-time delivery schemes with favored shippers, a circumstance that will require full time attention by logistics people and production managers.
Bad customers want the transaction to follow their particular terms and conditions. Bad customers will want 60 days net- a particularly transparent scheme to float their resources in interest bearing accounts while the vendor has to finance manufacture up front. The fetid odor of MBA finance people lingers here.
Bad customers will want their vendors to provide indemnity to shield them against any conceivable liability related to the product. Bad customers will want to own any and all inventions pertaining to process improvements relating to the product. They’ll want to be free to take this improvement and hand it to your competitors in order to generate a tidy little bidding war over their business.
Practices that I have been calling “bad” are generally accepted in the business world. On the buy-side they are considered good practices. On the sell-side they are arguably bad practices because they increase risk and expense related to the transaction. A good buyer tries to implement these bad attributes. A good seller tries to eliminate or minimize these bad attributes.
In the real world, one rarely has the option of walking away from bad customers. But it is possible to stand firm and prevent profit erosion. Very often a customers apparent demand is just a straw man. If not entirely a bluff, it might be negotiable to some reasonable concession. The best practice is to be up front with your concerns and communicate with the customer. They are nearly always reasonable.
The 80/20 rule often applies to customer service: 20 % of your customers will take 80 % of your time. This is life in the fabulous world of sales. Every sales person must eventually come to terms with it. Sales consultants talk about “qualifying” sales prospects, but that only applies to real estate and vacuum cleaners. The world of custom business-to-business chemical sales is such that if someone can identify your product and seek your services, they are almost always a legitimate player.
One of my most prized books is a tattered copy of Grignard Reactions of Nonmetallic Substances, by M.S. Kharasch and Otto Reinmuth, published in 1954 by Prentice-Hall. It is a 1384 page tome containing a vast number of examples of Grignard reagent chemistry and reaction chemistry with extensive references through 1954.
Morris Selig Kharasch was a professor at the University of Chicago and is primarily known for his work with free radical chemistry. To Kharasch is credited much of the early work in sorting out the mechanism of anti-Markovnikov addition of HBr to olefins. Reinmuth was the second Editor of the Journal of Chemical Education (1933-40). Two coworkers, Frank Mayo and Cheves Walling, went on to make contributions toward the development of vinyl polymerization.
Later in his career Kharasch turned to the examination of the Grignard reagent and many of its reactions. Among the list of his students and post-docs are H.C. Brown and George Buchi. Kharasch was instrumental in the founding of the Journal of Organic Chemistry and served on the Editorial Board for many years.
It is interesting to note that Kharasch is credited with the patenting of Thimerosal in 1927, a product also known under the trade name Merthiolate which has been used as an antimicrobial additive in vaccines.
I am one of the odd characters who rather admires lawyers. I have had a few occasions to be on both sides of a lawyers gun barrel and have come to admire them as a group for what they do. Contrary to what most people believe, they do much more than simply provide exquisite obfuscation. Yes, they can generate plenty of fear, doubt, and anger. Divorce lawyers generally have a stable of enemies. But more to the point they are trained to drill down to the facts of the case. They can pierce through the knotted fur ball of imperfect memory and slanted testamony to find the thread that connects the facts. Well, at least some of them can.
But what is perhaps more interesting than how lawyers perform is how their clients behave around them. If two parties are trying to plow through a complex negotiation without lawyers, for instance, it is likely that the tone of the proceedings will differ from a meeting with lawyers present. It is practically axiomatic that once one side has their attorney present, the other side feels compelled to have theirs present as well. This only makes sense. If the meeting concerns contractual issues or matters of liability or indemnity, it is best to have some legal firepower to oversee agreements or disclosures.
What happens when the attorneys are present is this. Like a startled bivalve, each side clamps down their shell and communication becomes a thin gruel of vague and hesitant exchanges. Suddenly everthing takes twice as long because both sides have to hunker down with counsel to discuss the plan off-line. Everyone is afraid of a slip up. Representatives of each company not only fear the other sides attorney, but their own as well. They fear the other sides attorney for advantages they might seize, but fear their own attorney for the consequences of a blunder on their side. Your own attorney will be able to describe your blunder in living color to management in the postmortem, so everyone is super cautious.
What is often missing in negotiations involving lawyers is plain talk. It often happens that in trying to be careful with disclosures and declarative statements, both sides fail to actually make a clear statement of what they want. Consequently, each side ends up negotiating a slightly different problem. It can take multiple meetings before everyone is on the same page negotiating the same deal.
Sales people are configured by nature to bring home the deal. They are inclined to do and say what it takes to git’er done. Procurement people are coy by nature and acclimated to their companies policy on purchasing. They want the best price, terms, and delivery possible. They will want concessions from the vendor and firm agreements on inventory and pricing schedules. They want and want and want. But in the end they have to get. They have to make the deal because raw materials have to arrive before invoices can go out for finished goods.
In negotiation, both sides bring their magic to the table. When lawyers are present, in my experience at least, everyone becomes so bloody careful and hesitant that a spirit of distrust can form. People become reticent to engage in plain talk. Lawyers are concerned with the “what if’s” and in fact it is their duty to make their client aware of such things. Soon after the lawyers jump in, people begin behaving like first year medical students who startle at every twinge and sniff.
The lawyers bring up the issues, but it is the duty of the experienced business manager to step back and assess the likelihood of a breach. The mistake people often make is to get the lawyer to make the decision for them rather than use the lawyers input to assess the big picture. The lawyer gets paid irrespective of the outcome of the decision. In the end, the business person must make the business decision and live with it.
Because lawyers are involved in key negotiations, they accumulate considerable “combat time” in business transactions. This is partly why lawyers end up on the board of directors of corporations. People feel more comfortable having them in the loop for the dicey decisions.
Lamentations on Chemistry 