William von Eggers Doering's Remarkable Career - Personal Observations from the 1950s and '60s "... the questions themselves" Rainer Maria Rilke RONALD M. MAGID AND MAITLAND JONES, JR. Department of Chemistry, The University of Tennessee; Department of Chemistry, New York University Received Dedicated to Professor Bill Doering on the occasion of his 90th birthday ______________________________________________________________ ABSTRACT This Account consists of reminiscences about the Doering research group at Yale University, nearly a half-century ago. We recount vignettes and events that reflect the state of research in physical organic chemistry at that early time, the passion that drove Doering, and the lessons that he taught to his coworkers. We allude to specific research results that are described in considerable detail in the preceding article. _________________________________________________________________ In the accompanying article1 we describe some of the truly remarkable research accomplishments by Bill Doering and his coworkers over a 60-year-span. An editor, who may yet regret it, thought that it would be interesting to include some reminiscences by two of Bill's former graduate students. It was suggested that they might focus on the human side of the equation: what made Doering tick, how did the research group function, what was the nature of physical organic chemistry research and equipment in the 1950s-60s, etc. RMM and MJJr are the co-authors of this Account. Both were Yale undergraduates in Bill's introductory organic course in Spring-Fall, 1957, and both did their graduate work under Bill's supervision. MJJr's knowledge of Doering both precedes and supercedes the 1957-1963 period. Even before college, he had spent some summers at Hickrill Chemical Research Laboratory (about which much more, soon). Then, during his years on the Princeton faculty, Mait maintained a close relationship with his 2 mentor. Most of what follows was written jointly by the two of us. Some sections, however, bear the authorship of just one of the pair - these will be clearly identified. I (MJJr) did indeed know Bill well before I even knew that chemistry existed, and I worked several summers at Hickrill, in Katonah New York. My parents lived nearby, knew Bill socially, and were anxious to find a job to keep their son off the street, or at least off the tennis court. Bill was kind enough to take on a totally inexperienced kid in a variety of probably make-work jobs. Most organic chemists will know of the absolutely fabulous work that came from that place - much of it the result of the Bill’s collaboration with the great, underappreciated Larry Knox - the tropylium ion and much of the early carbene work are only two examples. Hickrill had an ever-changing staff of postdocs, many of them from Europe, all overseen by Doering and a resident, “permanent” postdoc (Larry Knox). How could such a place come into being? When Doering joined Columbia in his first faculty position, there was, of course, a period of time when he was low man on the totem pole. At that time there was an unusual graduate student at Columbia, a middle-aged woman, Ruth Alice Weil, who had gone back to graduate school in chemistry. She found that the world of science didn’t exactly embrace such people with open arms, and wound up in the research group of the lowest-ranking person, Bill Doering. At some point, at what we used to call a bull-session (ahem), the question of “what would be the ideal home for research?” came up. When it came Bill’s turn to speak, he replied that he thought a smallish institute, with 5-10 postdocs, a resident majordomo and secure funding would be about right. Some time after the meeting, she came up to him and asked, “Did you mean it? if so, I’ll speak to my husband about it.” It turned out that they had zillions of dollars and they did it. Now I am not sure what the take-home lesson is here, but I find it delicious to imagine all the big daddies of the time walking the halls of the Columbia chemistry department smiting their foreheads. It’s a wonderful image. Hickrill certainly was “state of the art” at the time, but seems remarkably primitive 3 now. Instrumentation consisted of a Beckman UV, an early infrared spectrometer, a refractometer, and….that’s it. There was a wonderful library, looted, as were some of the labs, during clandestine nighttime raids from New Haven after Hickrill closed. Times were changing, though, and one of the early projects I can recall was the construction of a gas chromatograph – a preparative model, with a 2” wide column – and essentially no resolving power at all. It could hardly compete with the two-story fractional distillation column that ran from basement to the second floor – and was packed by MJJr at Doering’s command, “One glass helix at a time!” I cheated. The “wet” chemistry at Hickrill – and Yale - was also far different from that of today. For example, the scale of things was vastly larger. Need cycloheptatriene? You couldn’t buy it in those days, and you needed more than the fractions of milligrams we require today. The solution was to dissolve vast quantities of diazomethane in 12 L of benzene and blaze away with General Electric Sunlamps purchased at the hardware store. Low tech it may have been, but it made the molecule. The occasional fires, fueled by 12 L of burning benzene, are best not mentioned. Diazomethane was made from the notoriously dangerous N-nitroso-N-methyl urea (NMU) and 50% aqueous KOH (never NaOH, which was rumored to detonate diazomethane – or was it the other way round?). NMU itself was required in kilo amounts, and was synthesized in a metal garbage pail that was stirred with an old baseball bat; the solid NMU would rise to the surface and would be scooped away with a beaker in an ungloved hand. At Hickrill, it was my job to do that, as I seemed not very sensitive to NMU, and I recall bending over that hideous vat, which was bubbling, spitting, and emitting who knows what noxious molecules. At Yale, every new grad student was given this opportunity to achieve fame. Can you imagine that today? Everyone would be in jail. My role at Hickrill was something less than gopher, and I owe those folks, Larry Knox in particular, a great deal for putting up with me. The effect on a young person is easy to imagine. I didn’t know what anyone was really doing, and I vividly recall looking at the blackboard and trying to work out all the crossing lines of norbornanes and what 4 they meant. Nonetheless, the effect on me was enormous - literally life-determining, and that may stand as a metaphor for the impact Hickrill had on many people and, indeed, for the impact Bill Doering has had on so many of his students and associates. Like Hickrill, and of much broader impact in that it affected hundreds of students, Doering’s sophomore organic course at Yale was another powerful magnet attracting young people to organic chemistry, even those who were somewhat turned off by their previous experiences with chemistry. For example, I (RMM) was definitely put off by Yale's introductory course for chem majors - it was classical, descriptive, lacking in any theory, and dull – there was no excitement, no sense of passion whatsoever. I had been juggling the possibility of majoring in physics or math or chemistry - by the end of my freshman year, I was ready to commit to one of the first two, but MJJr convinced me to defer my decision for another semester or two. The first term of our sophomore year featured quantitative analysis; as Yale had (and still has) no analytical chemists on the faculty, the teaching of this course fell to the youngest physical chemist on the staff, who enjoyed being in the classroom and lab almost as little as we did. That solidified my decision to get out, but MJJr, who knew that I would be enthralled by Doering's course, urged me to stick it out. And so I did. And I fell in love - with the subject matter and with the man who let it unfold in glorious technicolor (at least five different colored pieces of chalk were employed every lecture) with witty dialog and extraordinary insights. I think that Bill loved teaching the undergrads as much as we loved being in his class. We soaked up the lessons and stories, bordering in many cases on the libelous. We were treated to remarkably candid comments about some famous organic chemists: "His head is filled with homogenized goose feathers" and "He's a throw-back to a Neanderthal" and "Thank goodness he's dead." We ate it up, as undergrads will, and as it was intended to be. Many alumni of Doering’s Chem 29/35 went on to become professors of chemistry themselves; it is a near-certainty that their lecture notes, style of delivery, and blackboard technique are patterned so closely after Doering’s that the fine line between flattery and plagiarism may well have been breached. 5 Did we know that even in his late 30's he was already one of the leading organic chemists of the world? Like other undergrads, most of us had very little understanding of the nature of academic research. And, in striking contrast to the open-door policy that Mait and I employed throughout our teaching careers, I don't recall ever having visited Doering in his office to ask questions.