of sodium oxalate's utility in CFC destruction is an outgrowth of a project aimed at finding better ways to partially defluorinate cyclic perfluorocarbons (C&EN, Oct. 23, 1995, page 26). "We looked for a two-electron reducing agent, on the grounds that fluoroalkenes are stabler intermediates than are the radicals that would be formed in a one-electron reduction," they explain in Science. "We wanted to combine the reductant with a fluoride-abstracting component, such as a metal cation." Burdeniuc, whom Crabtree describes as "a really inventive guy," was the one who thought of trying sodium ox-
alate. "Nobody would have given him any money to study that because sodium oxalate is such a wimpy reagent," Crabtree remarks. No one would have thought it would react with perfluoroalkanes, among the most refractory of all compounds, he adds. But once the Yale chemists saw how well the oxalate reaction worked with perfluorocarbons, Crabtree suggested trying it with CFCs. A variety of defluorination reagents had been developed previously, but they typically are expensive, inconvenient to use, or difficult to stop at the partial-defluorination stage. In commer-
Dow-Eli Lilly venture buys stake in Mycogen DowElanco—an agricultural products company that is a joint venture between Dow Chemical and Eli Lilly—will pay $152 million in cash and turn over its seed business to acquire a 46% stake in Mycogen, a San Diego-based agricultural biotechnology company. DowElanco, based in Indianapolis, has about $2 billion in worldwide annual sales. Dow Chemical owns a 60% share and Eli Lilly owns 40%. To gain its stake in Mycogen, DowElanco will purchase 9.5 million shares currently owned by Lubrizol, which is Mycogen's largest shareholder. These shares include 3.4 million newly issued shares resulting from Lubrizol· s conversion of its 19.5% interest in Mycogen's seed business and its holding of $31.6 million worth of Mycogen preferred stock. As part of the deal, Mycogen will acquire DowElanco's United AgriSeeds
Mycogen at a glance Revenues: $113 million in fiscal 1995a Net loss: $15.9 million in fiscal 1995a Headquarters: San Diego Founded: December 1982 Employees: 770; acquisition will add 200 from DowElanco's United AgriSeeds business Major product areas: Genetically enhanced pest-resistant seeds for crops, biopesticides, and crop protection services a Fiscal year ending Aug. 31, 1995.
business. Mycogen will exchange about 4.5 million newly issued shares of its common stock for the seed business and about $26 million in cash from DowElanco. Combined sales for United AgriSeeds and Mycogen's existing seed business would have exceeded $100 million in 1995. Mycogen also will spend $8 million to reacquire certain rights in oil seed technology from Lubrizol. Lubrizol, no longer considering Mycogen a strategic fit with its other businesses, will be cashing out its entire investment in the company. The two companies have been allied since 1987, when Lubrizol signed R&D contracts with Mycogen and bought a 16% stake. In 1992, Mycogen took a majority share in Lubrizol's Agrigenetics seed division. Mycogen also has marketing and R&D alliances with the Ciba Seeds division of Ciba-Geigy, with Japanese companies Kubota Corp. and Japan Tobacco, and with U.S. seed producer Pioneer Hi-Bred. The Mycogen deal will be DowElanco's largest biotechnology alliance to date, says a company spokesman. The firm has taken small equity positions in U.K.-based AGC, and in Boulder, Colo.based RPI, as well as set up research agreements with universities. DowElanco's 1988 acquisition of United AgriSeeds gave the company in-house biotechnology research capabilities. "This alliance is a major step forward in biotechnology for DowElanco," says President and Chief Executive Officer John Hagaman. "We believe that biotechnology will play a very major role in the development of future products for agriculture and offers multiple areas of substantial opportunity." For example,
cial operations, iron or nickel is often used at 450 to 500 °C, but this produces metal fluoride that requires disposal. One of the advantages of the oxalate reaction is that it allows partial defluorination of a saturated ring system. For example, the Yale researchers can convert perfluorodecalin into two different aromatic products: perfluorotetralin, which results from loss of six fluorine atoms, and perfluoronaphthalene, which results from loss of 10 fluorines. The reaction conditions can be tailored to produce more perfluorotetralin than perfluoronaphthalene. Ron Dagani last August Mycogen received Environmental Protection Agency approval to begin marketing seed corn genetically engineered for resistance to the European corn borer, a major corn pest. When the transaction is completed, DowElanco will own about 14 million of Mycogen's 30.4 million outstanding shares and will have the right to acquire additional shares. The deal is similar to one struck last October between Monsanto and Calgene, a Davis, Calif.-based agricultural biotechnology company. Ann Thayer
New technique boosts diamondfilmdeposition A small, privately held company in Dearborn, Mich., has achieved a major breakthrough in deposition of diamond films on a wide variety of materials. QQC Inc.—an affiliate of machine tool maker Turchan Inc.—has developed a technique that inexpensively deposits diamond films of varying thicknesses in a process analogous to spraying paint on a surface. Metallurgist Pravin Mistry, QQC president, came upon the technique two years ago. The coating is done at room temperature—without the vacuum, 700 to 1,000 °C temperatures, and hydrogen atmosphere needed in the standard chemical vapor deposition technique. Three lasers, whose pulses are coordinated by computer, supply energy for the deposition. The reaction milieu consists of variable proportions of carbon dioxide, which is the carbon source, and nitrogen. Robots guide the movement of the surface as the coating is applied. JANUARY 22,1996 C&EN
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NEWS OF THE WEEK No major announcement of the development has been made, and no detailed research reports have been presented to a scientific audience. But Mistry—who left Imperial College, London, before obtaining a degree—presented his work last August at the National Institute of Standards & Technology. He also described it last month at a diamond film conference in Barcelona, Spain. The work drew the attention of scientists at the Materials Research Laboratory at Pennsylvania State University, a leading center for research on diamond film technology. Penn State's Rustum Roy has arranged for the lab to study the mechanism. An agreement was about to be signed last week. "It is absolutely one of the biggest developments in materials synthesis in a generation," says Roy. "And the amazing thing is that it was done entirely as part of a production, not a research, process." A memo by a consultant for the Pentagon's Institute for Defense Analysis says government support for research on Mistr/s work should proceed "aggressively, optimistically, and rapidly." Two leading diamond film researchers contacted by C&EN would not comment on the development for lack of information. However, an official at the Office of Naval Research, who visited QQC, tells C&EN that the office intends to support research on the process. Test results that he saw confirmed that the coatings were diamond films. Mistry's achievement is one of those serendipitous developments that occasionally results from an error. In 1994, while working for another company, Mistry was supervising the titanium diboride coating of a die used for extrusion of aluminum tubing. The work involved "shrouding" the laser-induced coating environment in nitrogen gas. By mistake, nitrogen was replaced by carbon dioxide. When the coating process was finished, Mistry, to his astonishment, found that the die was coated with something resembling diamond film—much superior in properties to the intended titanium diboride. The deposition mechanism is not yet known. But Roy says the laser pulses likely raise the temperature at the substrate surface to about 10,000 °C, creating the plasma needed to produce the diamond crystal arrangement and to interlock it with the substrate surface. Soon after his accidental achieve8
JANUARY 22,1996 C&EN
ment, Mistry met Manuel Turchan, president of Turchan Inc., who was looking for cheaper and more environmentally benign ways of machining aluminum engine blocks for the auto industry. The process at the time involved continuous application of toxic lubricants to cool the areas where carbide-coated belts and drills met the metal. Mistry coated the carbide spindles and milling cutters with diamond film using the C02-laser technique, resulting in excellent performance without the lubricant complications. While the breakthrough in machine tool technology is significant, it is in the diamond film field where the current excitement lies. Mistry says the new process undoubtedly could replace the vapor deposition methods industry currently uses for diamond coating. Turchan Inc. has big plans for its diamond-coated machine tools business. The company has already applied for 63 patents on various aspects of the process. Last week, QQC and the Delphi Division of General Motors signed an agreement to coat brake rotors with diamond film. And Gillette is examining the process for application to razor blades. In all, more than 1,000 companies and organizations have expressed interest. Wil Lepkowski
Drugmakers seek reform in drug approval U.S. pharmaceutical manufacturers say they are pleased with recent progress by the Food & Drug Administration in speeding up its drug approval process, but the system is not yet good enough. Further reforms are needed, and drugmakers are supporting legislation to mandate those changes. In its annual review of new drug approvals, held last week in Washington, D.C., the Pharmaceutical Research & Manufacturers of America (PhRMA) challenged FDA's claim that its drug approval process is not a problem. "FDA's progress in reducing overall review time and the reforms it has announced the past year should not be allowed to obscure the fact that drug regulations in the U.S. must be reengineered," said PhRMA President Gerald J. Mossinghoff. FDA Commissioner David A. Kessler
Mossinghoff: enact fundamental reform has said there is no "drug lag" between the U.S. and other developed countries when it comes to new drug approvals. Kessler's assertion that the lag is a "myth" supports his contention that major reforms are not needed at the agency. Mossinghoff said FDA has reduced its review time for new drugs from an average of 19.7 months in 1994 to 19.2 months in 1995. "But this is still more than one year longer than the statutory standard enacted 30 years ago," he pointed out. He attributed the improvement i n review times to user fees paid by the pharmaceutical companies, which gave FDA the funds to hire more reviewers. The user fee legislation was passed in 1992. The problem is, he stressed, that more than 50% of new drug discoveries are made in the U.S., but about two-thirds of the drugs approved in the U.S. were approved first abroad. PhRMA figures show that of 28 new drugs approved in the U.S. in 1995, only 10 were approved there first. Over the past six years, 66% of new drugs approved in the world were first approved outside the U.S. Moreover, the time to bring a new drug from lab to marketplace has increased from about eight years in the 1960s to nearly 15 years today, according to a study by Tufts University. This increase has been accompanied by continued expansion of R&D costs. PhRMA reports that drugmakers invested $14.4 billion in R&D in 1995, up from $13.4 billion in 1994. This year, PhRMA predicts, companies will spend a record $15.8 billion for R&D, 19% of estimated 1996 pharmaceutical sales. The U.S. will lead the world in drug approvals "only when we enact fundamental FDA reform legislation," Moss-
