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HOWARD ENSIGN SIMMONS, JR. June 1 7, 1 929-April 26, 1997 BY JOHN D. ROBERTS AND JOHN W. COLLETTE IN THE CURRENT PERIOD where almost all large U.S. corpora- tions have clownsizec! their research efforts en c! traclec! most of their long-term basic research for short-term gain at the bottom line, it is relevant to consider the scientific en c! management career, as well as the life, of one of the leacling inclustrial research scientists of the twentieth cen- tury, who was cleeply involves! in the time of changing views of corporations towarc! basic research. Howarc! Ensign Simmons, {r., was born in Norfolk, Vir- ginia, on June 17, 1929. His father en c! his uncles were sea captains, but his father clic! not encourage him to follow that career, instead, he helpec! with Howarcl's desire to stucly chemistry, starting at age twelve, by builcling him a small but well-usec! laboratory as an aciclition to their home. Howarcl's mother came from a family with a different bent. Her parents emigratec! from Bavaria, en c! her father was an entomologist, possibly inspirer! by one of his forebears, Jacob Hubner (1761-1826), characterizec! as the first great lepi- clopterist, who compiler! the first catalog of North Ameri- can butterflies. By his own account, Howarc! clic! not clo too well in his early schooling until he encountered Latin en c! other lan- guages, the stucly of which he fount! very interesting, en c! 315

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316 BIOGRAPHICAL MEMOIRS incleec! became a lifelong avocation. He clic! so well at French in high school that he was offerer! a scholarship at the University of Virginia, but with his interest in science he cleciclec! to go to MIT. Howarc! saw MIT as a true Mecca of science with its aura of scientific en c! engineering prowess greatly enhancer! by its success in war research. Howarc! enterer! MIT in 1947, joiner! en c! liver! in a social fraternity, en c! enrollee! in the ROTC. He starter! somewhat slowly aca- clemically, but was at the top of the chemistry class by the time he gracluatecI. In this periocI, MIT hac! a senior-thesis requirement en c! Howarc! clic! exemplary research in organic chemistry with I. D. Roberts on the mechanism of the reaction of silver salts of carboxylic acicis with incline. The heat! of the Chem- istry Department, Arthur C. Cope, was endeavoring to im- prove the quality and diversity of the organic chemistry graduate students en c! believer! that the best way to clo that was to require MIT unclergracluates to go elsewhere for graclu- ate work. On occasion, he was willing to relax this require- ment and, in one particular periocI, three outstanding ex- ceptions were E. I. Corey (Nobel Prize in chemistry, 1990), Robert H. Mazur (later the discoverer of NutraSweet), en c! Howarc! E. Simmons, {r. Simmons made a very successful start on his graduate thesis work in which he continues! with l. D. Roberts on the chemistry of cyclobutenones. But that work was suspenclec! so that Howarc! conic! investigate the intermediacy of benzyne (benzene minus two hycirogens, C6H4) by the removal of HCl from chIorobenzene with the strongly basic reagent, sodium amide. Howarc! playact a crucial rule in this achieve- ment, which is immortalized in almost every elementary textbook, not only as evidence for benzyne but also as a prime example of the use of isotopic labeling to establish a reaction mechanism.

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HOWARD ENSIGN SIMMONS, JR. H H ,//\rH Hi/-CI H 317 H NaNH2 H : -NH3-NaCI , H benzyne When his thesis supervisor cleciclec! to move to a profes- sorship at the California Institute of Technology, Howarc! electec! to remain at MIT en c! complete his doctorate work with Arthur Cope on cyclooctane chemistry. In all, Howarcl's Ph.D. research resultec! in six publications in quite diverse fielcis of organic chemistry. Although he wouic! have been a prime cancliciate for a postcloctoral fellowship or a junior academic position when he finisher! his Ph.D., Howarc! acceptec! a position in the Chemical Department (subsequently the Central Research Department) of the DuPont Company in 1954. This was cluring a perioc! later referrer! to as the goIclen age of basic research at DuPont. At that time, the company hac! well- establishec! businesses in fibers (nylon, Dacron~, OrIon~), films (cellophane, Mylar~), plastics (polyethylene, Teflon~), neoprene elastomer, tetraethyIleacI, automotive finishes, re- frigerants, ant! many basic chemicals, as well as owning more than 20% of General Motors Corporation. The success of the research of Wallace H. Carothers2 before Woric! War II with nylon, along with the clemonstratec! utility of what hac! been consiclerec! purely academic research to the war ef- fort, spawner! a euphoria of what basic research conic! achieve at DuPont's inclustrial laboratories in the way of "Better things for better living through Chemistry." In this period,

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318 BIOGRAPHICAL MEMOIRS well before the magnificent array of DuPont products be- came commonplace, the company was clearly ensconces! in the public's mine! as a provider of technological miracles. DuPont's research in the early 1950s when Simmons came aboarc! was by no means concentrates! in the Central Re- search Department. Absolutely outstanding exploratory re- search was being carrier! out in the Organic Chemicals, Polychemicals, Explosives, Photo Products, Pigments, Tex- tile Fibers, Agricultural Chemicals, en c! Electrochemicals Departments that were the mainstays of DuPont's businesses. An c! much of that research was publisher! or presenter! at professional meetings. The success of the research in the manufacturing clepart ments in support of their businesses, along with an upper management decision to make Central Research inclepen- dent of the operating departments, provided Central Re- search the opportunity to engage in many basic research programs that became the envy of the university chemical community. This is not to say that Central Research pro- grams failer! to be clirectec! towarc! new businesses for DuPont. The objectives were in place, but a principal focus was taken on the clevelopment of new chemistry, rather than incre- mental improvement of existing processes. The emphasis on entirely new chemistry was surely in- spirec! by a number of extraordinary discoveries that shook up conventional icleas of what was possible in organic chem- istry. One was the discovery in Germany of cyclic polymer- ization of acetylene to provicle any clesirec! quantity of cyclooctatetracne, a substance macle earlier in very small amounts that turner! out later to undergo a plethora of quite unexpected chemical transformations.

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HOWARD ENSIGN SIMMONS, JR. \.=./ cyclooctatetracne 319 Another was the unusual properties found for highly fluori- natec! substances. Still another was the discovery in Englanc! of ferrocene en c! its wholly unanticipated! properties. Fer- rocene was later shown to have a structure with an iron atom sanc~wichec! symmetrically between two five-memberec! carbon rings. ferrocene This latter fincling lee! to an entirely new field! of organo- metallic chemistry that has proclucec! many new catalysts for diverse reactions of prime inclustrial utility. In this arena, DuPont playact a very significant role. As we have said, the goal of DuPont's Central Research in this yeasty period! was to produce new chemistry en c! new chemicals. Particular emphasis was to be placer! on organic chemicals and, in one way, this was particularly appropri- ate, because before en c! until a few years after Woric! War II, research in organic chemistry clic! not require substan- tial capital investments. This was true despite enormous growth in the knowlecige en c! utility of organic chemistry, as well as the clevelopment of new reactions, because little

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320 change in the techn handling of organic chemistry had occurred over the previ- ous fifty years. But, unforeseen en c! enormous changes were in the wincI. One was the ongoing development of highly sophisticated techniques applicable to the analysis of organic compounds, such as visible and ultraviolet spectroscopy, gas- and liquid- phase chromatography, mass spectroscopy, routine crystal- lographic structural analyses, infrarec! en c! Raman spectros- copy, and, perhaps more than any other, nuclear magnetic resonance (NMR) spectroscopy. Central Research, by virtue of its charter, sought to be in the forefront in investigating these techniques en c! clemon- strating their value for inclustrial research. With NMR, DuPont playact a major role in the clevelopment of its uses for analysis en c! structural characterization, primarily through the work of William D. Phillips.3 Instruments of this character, while enormously increasing the efficiency of organic research, require investment of millions of clollars in technologies utilizing equipment that becomes essentially obsolete en c! neecis to be upgraclec! or replacer! in three-to five-year cycles, BIOGRAPHICAL MEMOIRS 1i aquas available for characterization or much in the same way as many of us continually encounter on a smaller scale with personal computers. Aciclitional research costs also resultec! from greater em- phasis on laboratory safety, an area in which DuPont has always maintainer! a leaclership position, as well as changes in laboratory practices clesignec! to meet societal concerns for emissions and disposal of laboratory wastes. These ant! other problems were to confront Howarc! Simmons in his steaclily upwarc! career at the Central Re- search Department. However, early on, the focus was on synthesis en c! stucly of entirely new compositions of matter. although perhaps with some degree of overconfidence that profitable uses conic! be fount! for these materials as they

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HOWARD ENSIGN SIMMONS, JR. 32 became available. Right from the outset, Simmons clevel- opec! new chemistry. His early work features! a keen inter- est in using highly reactive intermediates in synthesis. He hac! fount! a reference to the formation of a gas in the reaction of CH2I2 with zinc en c! investigates! the possibility that the gas could be ethylene, CH2=CH2, formed by dimer- ization of unstable carbene, CH2. A cletailec! stucly of the reaction lee! to a very general synthesis of cyclopropanes, derivatives of the three-memberec! carbon ring, (CHIN, now universally known as the Simmons-Smith reaction. One of Howarcl's collaborators on studies of the mechanism of this reaction was E. P. ("Doc") BlancharcI, who later became a vice-chairman of the company. 3 + cH2 12 ~ Zn(Cu) Simmons-Smith reaction ACHE A later project involves! further eTuciciation of the struc- ture of benzyne and, to this end, he concluctec! trapping experiments of this very unstable intermediate that lee! him to conclucle that benzyne is truly aromatic in the same sense as benzene, but has a very reactive multiple bond. This conclusion remains the prevailing view to this clay, although much more is now known about benzyne, en c! even its NMR spectrum has been taken.4 A discussion of some elements of the culture of DuPont's Central Research Department in Howarcl's time is perhaps worthy of mention here. One still adherer! to is that re- search chemists (often clesignec! as "bench" chemists), with very few exceptions, carry on their work with the assistance of technicians possessing different levels of skill en c! experi

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322 BIOGRAPHICAL MEMOIRS once. Normally, there is no way for chemists at this level to multiply their research output by having more than one technician. Promotion to research supervisor is necessary, en c! then the chemist acquires an office en c! a research group that works on the supervisor's icleas to quite varying degrees. Much clepencis on the research creclentials of the supervisor, en c! in Howarcl's case they were very high. Many of those who came to CRD often cleciclec! that their chances for promotion en c! influence in the company were better if they transferred! to an operating department, en c! this meant that the turnover was relatively high, which of course gave more opportunities for the department to search for en c! hire outstanding new Ph.D. recipients.5 In recent years, trans fers have become less common and, as a result, with the sIowclown of hiring generally, the average age of the CRD personnel has risen consiclerably. At the same time, more technical responsibility for the direction of research has shifter! to the chemist as the result of having to carry out short-term projects in support of the company's business units. An open-cloor policy was also a feature of the Central Research Department culture when Simmons came. This meant that, even up to the research director, everyone's floor was kept open at all times unless conficlential matters were being cliscussecI. It was a great policy for really com- munication en c! goof! feelings, but not so satisfactory for contemplative study of difficult problems. Simmons made a conscious en c! successful decision on his own to change the culture. It was not altogether popular with the manage- ment, but he was so goof! that he macle it stick. Despite this, all of his colleagues regarded him as being very acces- sible and helpful with their problems. Another consideration for Central Research was publica- tion policy. It is customary for inclustrial research laborato

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HOWARD ENSIGN SIMMONS, JR. 323 ries to be wary of publication in the open literature, en c! many in DuPont opposer! CRD's quite vigorous policy of clisplaying its technical achievements at scientific meetings en c! in the scientific literature. Some take the view that, even if publication cloes not actually air! a competitor's cle velopment or improvement of a commercial process, open publication conic! give valuable indications to a competitor as to where DuPont's research was howling. Further, there is the question of compromising patent protection, and, in Howarcl's case, the opportunities to patent the Simmons- Smith reactions were in fact limiter! by early publication of the results.5 To reconcile the concerns of the operating departments with regard to the importance given to publication by CRD management, a system was establisher! of circulating pro- posec! publications to the operating departments for non- objection to, if not outright approval of, before sencling the manuscripts to journals.5 There can be no doubt that the Central Research publication policy was a fabulous success for recruiting talentec! young chemists. During the perioc! when Simmons was active, many graduate students believer! that the best research positions anywhere that one conic! aspire to were at the very few top universities en c! DuPont's Central Research. Another sticky issue that Simmons helpec! to resolve re- garclec! whose names shouIc! appear as co-authors on CRD publications. Some of the supervisors who clic! not actually participate in particular research projects but hac! aciminis- trative responsibility over them, felt that they shouIc! be incluclec! among the authors. This clic! not sit too well with the chemists clirectly involves! en c! a practice was establisher! to inclucle only those who actually participated. It was true, however, that if the authoress wished, others conic! be af- forclec! courtesy authorship.5

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324 BIOGRAPHICAL MEMOIRS A wonclerfuT international relation-buiTcling policy carrier! out by CRD cluring the Simmons era was to invite foreign chemists to come to the Uniter! States, not only to visit CRD but also to spenc! some time with university chemistry departments giving lectures ant! getting acquainted. Simmons macle visits to Europe to search for the rising research stars to implement this policy, which clevelopec! many Tong-last- ing relationships.5 As research supervisor, Simmons continues! the stucly of unusual intermediates now of cyanonitrene, a substance former! by heating cyanogen azicle. N=N=N-C-N heat. N-N ~ N=C=N cyanonitrene Cyanonitrene was fount! to provicle access to a variety of cyan o-substitute c! pro ducts by aciclition to aromatic hyciro- carbons, alkanes, en c! alkenes. Simmons user! isotopic la- beling to show that cyanogen azicle reacts with alkenes be- fore losing No, but with aromatics en c! alkanes, cyanonitrene with two chemically equivalent nitrogens is the intermedi- ate. Further, he clemonstratec! that cyanonitrene is initially former! in a singlet state en c! then decays with a measurable half-life to a more stable triplet state. During the 1960s en c! 1970s, the Central Research De- partment hac! an extensive program uncler the direction of T. L. Cairns to synthesize long-chain cyanocarbons, substances analogous to Tong-chain fluorocarbons, such as TeflonO.

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HOWARD ENSIGN SIMMONS, JR. 329 many DuPont en c! DuPont-Merck personnel working sicle by sicle in the Central Research laboratories. The thrust into materials science was characterizes! by research on new polymers, optical en c! electronic materials, high-temperature superconductors, en c! ceramics. These new efforts were carrier! on while maintaining strong core ef- forts in exploratory organic chemistry, physical chemistry, analytical techniques, en c! catalysis. The expansion is evi- clencec! by the scientific publications of the department, which increaser! from an average of 100 per year cluring 1975-79 to 200 per year during 1985-87, with major growth in biological en c! material sciences. During the Simmons perioc! as research director en c! vice- presiclent, the department playact a critical role in clevelop- ing practical catalytic processes to make hycirochIoro- fluorocarbons (HCFCs) to replace the chiorofluorocarbons (CFCs) implicates! in atmospheric-ozone clepletion, an im- portant societal neecI. Central Research was able to responc! because of its scientific depth in fluorocarbon chemistry en c! in catalysis. In the polymer field, group-transfer polymerization was cliscoverec! by O. Webster9 en c! was the first new polymeriza- tion process clevelopec! since living anionic polymerization. Not only was the mechanism of the reaction cleterminecI, but the process was converter! to commercial application in a relatively short time. The basic process of group transfer also has application to general organic synthesis, inclucling natural products. Other studies have involves! extension of theoretical mocleling to predict tensile properties of flex- ible- and rigid-chain polymers. The department clevelopec! new electronic en c! magnetic materials, especially potassium titany~phosphate, a most ver- satile nonlinear optical material. A major program was also

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330 BIOGRAPHICAL MEMOIRS carrier! on for the synthesis, characterization, en c! applica- tion of high-temperature superconductors. Molecular biology en c! agricultural biotechnology also re- ceivec! major attention, one output being advances in DNA- sequencing technology baser! on synthesis of novel fluores- cent labels. This effort also resultec! in Qualicon, a DuPont venture that identifies bacteria by examination of their DNA using PCR. Substantial success was also achiever! in the syn- thesis of unnatural pepticles en c! proteins to accomplish specific functions en c! precliction of their tertiary structures. DuPont was the first chemical company to obtain a Gray supercomputer en c! was in the forefront of use of super- computer applications in quantum chemistry in support of basic research, atmospheric moclels relevant to ozone cleple- tion, en c! theoretical moclels of material properties in com- plex multiphase systems. Over the forty years of the golden age of DuPont's basic research programs in the Central Research Department, the woric! was changing. New generations of the general public came to regard nylon, Teflon(~), Dacron(~), Mylar(~), and so on, not as technological wonclers but as commodities just as essential to moclern life as foocI, water, en c! power, but cle sirec! to be inexpensive, completely benign to human health no matter how used, en c! proclucec! by environmentally be- nign processes. However, as patents expires! en c! expertise in polymer technology became more wiclespreacI, global competition increased. Many more research-basec! compa- nies enterer! the polymer field! en c! new polymers aimec! at niche markets proliferated. Still other companies entered the field! by purchasing turnkey plants to manufacture ny- Ton en c! polyester. They conic! then compete with DuPont on a cost basis without making DuPont's large investment in research en c! market clevelopment. To be sure, many such operations lacked! the technical sawy to provicle the

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HOWARD ENSIGN SIMMONS, JR. 331 quality of DuPont's saTes-service support, but many custom- ers are willing to sacrifice quality of support for lower prices. With the rise of rampant en c! global competition along with a squeeze on profits en c! higher energy en c! environ- mental costs, it was clear that DuPont upper management was sure to ask, "What has all of this investment in Central Research clone for us?" Phrases like "research is a black hole into which you pour money" became common. One shouIc! not infer that the value of the work of Central Re- search to the company's bottom line was not questionec! earlier. Incleec! it was, en c! often. Notions that DuPont has hac! cluring the last half of this century an unwavering cor- porate strategy for the utilization of its research in sunnort- ing existing businesses en c! starting new ones clo not square with the facts.~ The company, driven by rapidly changing business climates in the last thirty years, has often been in internal upheavals, with multiple periods of reorganization swinging between concentration, on one hancI, on profit centers, strategic business units, en c! the like and, on the other hancI, to selling off existing businesses, new acquisi- tions (the largest, Conoco), en c! new ventures.~ ii Research has always felt the swells from these disturbances, but for a long perioc! these were mocleratecI, because upper manage- ment very largely hac! technical rather than business back- grouncis en c! recognizec! the new! for patience when the 1 1 leac! time between a laboratory discovery en c! a plant turn- ing out a product is often ten to fourteen years. It is certainly true that many new DuPont products were brought to the market between 1950 en c! 1980. To mention just a few, there were Norclel~, an oxiciation-resistant elas- tomer, LycraO, the popular spanclex fiber, DeirinO, polyacetal polymer, Viton~, a fluoropolymer elastomer, KevIar~ en c! Nomex~ aramic! fibers, Kapton~ polyimicle films, en c! tita- nium clioxicle paper en c! paint whiteners. Although of high

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332 BIOGRAPHICAL MEMOIRS quality en c! successful, these clic! not instantly capture the public imagination like nylon.2 if Instead, these products were born into an aIreacly crowclec! arena of polymers, macle woric~wicle and, to a substantial degree, they hac! to com- pete primarily in niche applications. The failure of the Central Research Department's over- abunciance of extraordinary new chemistry to provicle a cor- nucopia of stunning new products that conic! be commer- cializec! by the operating departments at acceptable costs en c! in acceptable time periods, along with the new! to make the manufacture of the company's existing line of products more efficient and more environmentally benign, as well as perceived neecis for better returns on stockhoicI- ers investment, lee! to many changes. Initially, a virtual hoIc! occurrec! on new hires in Central Research, then substan- tial downsizing en c! a refocusing of the research effort on immediate, rather than long-term, concerns. Simmons was already involved in management when Irv- ing Shapiro, a lawyer, became the head of the company and, when facet! with the Arab oil crisis en c! escalating raw material costs, macle substantial cuts in research. Business conditions were better when Shapiro was succeeclec! by EcI- warc! G. Jefferson, a Ph.D. chemist, who was a strong sup- porter of research and, as mentioner! above, brought about a very substantial expansion of CRD in life sciences. But this was not of itself a panacea for those chemists en c! su- pervisors who felt threatener! by expansion into areas in which they were unfamiliar. Simmons presided over CRD through several of the ups en c! clowns of changing views of the value of basic research en c! clic! his very best to clefenc! the work of the department, as well as to try to accommo- ciate to the new situations. However, after his retirement, he often expresser! private dissatisfaction with the extent to which the mission of the department changer! to focus on

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HOWARD ENSIGN SIMMONS, JR. 333 short-term gains, ant! this exacerbated his concern for DuPont's long-term future. Howarc! Simmons was an extraorclinarily interesting per- son with a quickness en c! intellectual power that was truly impressive. He hac! more than enough requisites to be suc- cessful in the academic worIcI, but he refuses! a number of offers of university professorships, inclucling MIT. He clic! participate in visiting professorships at Harvarc! en c! the University of Chicago, en c! he acceptec! an adjunct profes- sorship at the University of Delaware. He took professional responsibilities seriously, en c! servec! on advisory or execu- tive committees for the American Chemical Society, MIT, Harvard, Rensselaer, Franklin Institute, Los Alamos, Mary- lancI, University of California at San Diego, en c! Chicago. He was on the Advisory Boarc! en c! later president of the Boarc! of Trustees of the Chemical Heritage Foundation. Late in life, he was appointee! to the National Science Board, but ill health reclucec! his participation in the last part of his term. Simmons's scientific en c! management work was recog- nizec! by honorary degrees from Rensselaer en c! the Univer- sity of Delaware. He receiver! the ChancIler Mecial from Co- lumbia, the National Mecial of Science in 1992, en c! in 1994 both the Priestley Mecial, the highest aware! of the Ameri- can Chemical Society, en c! the Lavoisier Mecial of the DuPont Company, its highest aware! for technical achievement. He was electec! to the National Academy of Sciences in 1975 en c! the American Philosophical Society in 1990. Howarc! was a staunch political conservative with a high level of clisciain for most contemporary liberal thought. One conic! have almost bitter arguments with him on matters of political principles en c! outcomes, but, because these were on an intellectual rather than personal plane, one conic! remain a warm en c! fast friend. An omnivorous reacler,

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334 BIOGRAPHICAL MEMOIRS Howarc! was extraorclinariTy well informer! on a wicle range of subjects. From age twelve onward, Howarc! Simmons en c! Eliza- beth Warren grew up together in Norfolk. After the not- unusual teenage ups en c! clowns, they were marries! on Sep- tember I, 1951. Liz, as she is wiclely known, was a wonclerful partner in the Simmons enterprise. The couple hac! two sons, John W. en c! Howarc! E. Simmons III, both of whom earnec! Ph.D. degrees in organic chemistry, John at Yale, Howarc! at Harvard. They are employoc! at DuPont, John in DuPont Nylon en c! Howarc! at Central Research. Howarc! Simmons' views on physical exercise were appar- ently not far from those of ATexancler Woolicot's: "If I think about exercise, I know if I wait long enough, the thought will go away." But he clic! have a goocI-sizec! powerboat en c! fount! great happiness in overnight cruising on the Chesa- peake Bay. A heavy smoker for much of his life, Howarc! finally succumbec! after a long struggle to lung cancer en c! heart disease on April 26, 1997. Howarc! Ensign Simmons, {r., was a titan among chemists en c! his personal en c! scientific achievements will not soon be forgotten. WE WISH TO THANK Elizabeth Simmons and Howard E. Simmons III for their help in providing valuable information and insights for this memoir, as well as the Chemical Heritage Foundation for ac- cess to, and permission to use material from, their H. E. Simmons, Jr., oral history.5 Very helpful additional comments and suggestions were received from Edward G. Jefferson, E. P. Blanchard, Joseph H. Miller, Blaine C. McKusick, and Suzanne Grandel. We especially thank the Central Research Department of Du Pont for supplying and making possible publication of the accompanying color por- trait of Howard Simmons.

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HOWARD ENSIGN SIMMONS, JR. NOTES 335 1. T. D. Roberts and T. C. Sheehan. Arthur Clay Cope, 1909-1966. In Biographical Memoirs, vol. 60, pp. 16-30. Washington, D.C.: Na- tional Academy Press, 1991. 2. M. E. Hermes. Enough for One Lifetime. Wallace Carothers, Inven- tor of Nylon. Washington, D.C.: ACS Books, 1996. 3. R. C. Ferguson. William D. Phillips and nuclear magnetic reso- nance at DuPont. In Encyclopedia of Nuclear Magnetic Resonance, vol. 1, eds. D. M. Grant and R. K. Harris, pp. 309-13. Chichester, England: Tohn Wiley & Sons, 1996. 4. R. Warmuth. NMR of mbenzyne stabilized inside a molecular container compound: Is the species a strained alkyne or a cumulene? Angew. Chem. Int. Ed. 36 ~ 1997) :1347-50. 5. T. T. Bohning. Howard E. Simmons, fr., Oral History. Philadel- phia: Chemical Heritage Foundation, 1993. 6. C. G. Pedersen. The discovery of crown ethers. In Nobel Lec- tures in Chemistry (1981-1990J, ed. B. G. Malmstrom, pp. 495-511. Singapore: World Science, 1992. 7. L. A. Paquette. Dodecahedrane the chemical transliteration of Plato's Universe (a review) . 7. Am. Chem. Soc. 79 ~ 1982) :4495-4500. 8. R. G. Bergman, G. W. Parshall, and K. N. Raymond. Earl L. Muetterties, 1927-1984. In Biographical Memoirs, vol. 63, pp. 383-93. Washington, D.C.: National Academy Press, 1994. 9. O. W. Webster and coworkers. Group-transfer polymerization. 1. A new concept for addition polymerization with silicon initiators. I. Am. Chem. Soc. 105 ~ 1983) :5706-5708. 10. D. A. Hounshell and T. T. K. Smith. Science and Corporate Strat- egy. DuPont RED, 1902-1980. New York: Cambridge University Press, 1988. 11. Ibid. Part V, pp. 503-601, for an account of early struggles between research managers and non-research oriented managers over the importance of research to DuPont's long-term success. 12. For vivid descriptions of the public reaction to the initial sales of nylon stockings, see preface in Note 2 and pp. 268-71 in Note 10.

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336 BIOGRAPHICAL MEMOIRS SELECTED BIBLIOGRAPHY 1953 With J. D. Roberts, L. A. Carlsmith, and C. W. Vaughan. Rearrange- ment in the reaction of chlorobenzene-1-~4C with potassium amide. I. Am. Chem. Soc. 75: 3290-91. 1956 With J. D. Roberts, D. A. Semenow, and L. A. Carlsmith. The mechanism of aminations of halobenzenes. 7. Am. Chem. Soc. 78:601-11. 1958 With R. D. Smith. A new synthesis of cyclopropanes from olefins. 7. Am. Chem. Soc. 80:5323-24. 1960 With D. E. Wiley. Fluoroketones. I. 7. Am. Chem. Soc. 82:2288-96. 1961 A cycloaddition reaction of benzyne. 7. Am. Chem. Soc. 83:1657-64. 1964 Pariser-Parr theory: Quantum mechanical integrals from the ben- zene spectrum. 7. Chem. Phys. 40:3554-62. With J. K. Williams. An empirical model for nonbonded H-H repul- sion energies in hydrocarbons. J. Am. Chem. Soc. 86:3222-6. 1966 With S. Proskow and T. L. Cairns. Stereochemistry of the cycloaddi- tion reaction of 1,2-bis~trifluoromethyl)-1,2-dicyanoethylene and electron-rich alkenes. 7. Am. Chem. Soc. 88:5254-66. 1967 With R. A. Carboni, J. C. Kauer, and J. E. Castle. Aromatic azapentalenes. IV. f. Am. Chem. Soc. 89:2618-25. With A. G. Anastassiou. Cyanonitrene. A reaction with saturated hydrocarbons. 7. Am. Chem. Soc. 89:3177-84. With T. Fukunaga. Spiroconjugation. J. Am. Chem. Soc. 89:5208-15.

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HOWARD ENSIGN SIMMONS, JR. 1968 337 With C. H. Park. Macrobicyclic amines. I. Out-in isomerism of (l,k+2~- diazabicyclo~k.1.m~alkanes. 7. Am. Chem. Soc. 90:2428-29. With C. H. Park. Macrobicyclic amines. II. Out-out in-in prototropy in (l,k+2~-diazabicyclo ~k.1.m] alkane ammonium ions. 7. Am. Chem. Soc. 90:2429-31. With C. H. Park. Macrobicyclic amines. III. Encapsulation of halide ions by in-in-(l,k+2~-diazabicyclo ~k,l,m] alkane ammonium ions. [. Am. Chem. Soc. 90:2431-32. With J. C. Kauer. The tetramers of acetylenedicarboxylic esters. 7. Org. Chem. 33:2720-26. 1970 With C. H. Park, R. T. Uyeda, and M. Habibi. Macrobicyclic mol- ecules. Trans. N. Y. A cad. Sci. 32~5~:521. With A. G. Anastassiou, J. N. Shepelavy, and F. D. Marsh. Cyanonitrene. New York: Interscience Publishers. 1972 With C. H. Park. Bicyclo t8.8.8] hexacosane. Out-in isomerism. 7. Am. Chem. Soc. 94:7184-86. 1973 With T. L. Cairns, S. A. Vladuchick, and C. M. Hoiness. Cyclopro- panes from unsaturated compounds and methylene iodide and zinc-copper couple. Org. React. 20:1-131. 1974 With J. F. Bunnett. Orbital Symmetry Papers. Washington, D.C.: American Chemical Society Publishers. 1976 With M. D. Gordon and T. Fukunaga. A quantitative treatment of spiroconjugation. Long-range 'through-space' interactions and chemical reactivity of spirenes. 7. Am. Chem. Soc. 98:8401. 1980 With S. A. Vladuchick, T. Fukunaga, and O. W. Webster. Thiacyano- carbons. 6.1,4-dithiimo (2,3-c; 6,5-c')-diisothiazole 3,7-dicarbonitrile,

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338 BIOGRAPHICAL MEMOIRS isothiazole (3,4-f)-(1,2,3,4,5-pentathiepine-8-carbonitrile, and disodium 5-cyanoisothiazoledithiolate. 7. Org. Chem. 45:5122-30. 1983 With T. Fukunaga, T. T. Wendeloski, and M. D. Gordon. Trefoil aromatics: A potentially new class of aromatic molecules. 7. Am. Chem. Soc. 105:2729-34. 1 989 With R. E. Merrifield. Topological Methods in Chemistry. New York: Wiley Interscience.

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