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The Boron-Carbon Ring American Chemical Society Award in Petroleum Chemistry sponsored by Precision Scientific Company
ROBERT P. EISCHENS Both academic hydro carbon chemistry and the petroleum industry have benefited greatly from the new approaches to under standing catalysts devel oped by Robert P. Eischens, .winner of the AMERICAN CHEMICAL
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The discovery of a new class of compounds is always an event nf interest to theoInorganic retical chemists. Chemistry A n d when the n e w class of compounds i s in as active a field as that of boron chemistry, t h e interest is heightened. Thus the synthesis for t h e first time of boroncarbon ring compounds takes on special significance. Sheldon L. Clark and His fellow workers at Olin Mathieson have iso lated 1-n-butylboracyclopentane and 1-rî-butylboracyclohexane. Clark told t h e Division of Inorganic Chemistry's symposium—From Borax to Boranes— their method appears t o be a general one which should work for boron-carbon ring compounds of almost any chosen size. Clark reports that t h e ring-forming reaction was found during a t t e m p t s to pr epa re 1,4-bis(di-n-butylboryl)-butane and 1,5-bis ( di-n-butylboryl ) -pentane. T h e synthesis proposed for these compounds involved reaction between di-nbutylchloroborane and tetramethylene,ACS .NATIONAL ^MEETING
CIETY Award in Petroleum Chemistry. In Europe, as well as t h e U. S., his work on the infrared spec tra of adsorbed molecules is regarded as a significant advance in adsorption and Petroleum Chemistry Award winner Robert catalysis. Eischens h a s pioneered P. Eischens of Texaco (right) and Chester in three different lines: A. Warner of Precision Scientific magnetic susceptibility of Born in Glenmore Township, oxide catalysts, exchange reactions T of chemisorbed gases, and infrared N . D . , Eischens h a s his bachelor degree from University of Wisconsin spectra of chemisorbed molecules. Ph.D. from Northwestern. In t h e first, he developed the prin and ciples and methods for using mag Upon leaving graduate school he be netic susceptibility to study the gan h i s present employment in phys structure of supported oxide cata ical research at Texas Co.'s research lysts. H e also applied the method center, Beacon, Ν. Υ. Eischens has a strong and active of isotope exchange reactions in a new way to the study of carbon interest in political affairs both at monoxide chemisorbed on metal the local and national level. He has surfaces and to the problem of sur been a n active worker toward con solidating local schools. He be face heterogeneity. His exploratory work on the in came an active worker in the local frared spectra of chemisorbed mole Republican organization in 1952. cules has yielded direct information One of his personal contributions in on the nature of catalyst surfaces, the campaign was free rides on his chemisorbed species, and reaction horse to anyone w h o claimed to b e a n Eisenhower supporter. intermediates. Travel a n d small foreign cars are Eischens enjoys a controversial discussion with other scientists hav Eischens' ranking hobbies, but h e ing differing views. In such argu can seldom displace Mrs. Eischens ments, his own strong sense of humor from the wheel of his Citroen 2CV. is clearly revealed, a n d they are en Last year, when he drove his Citroen livened by his witty phrasing. One to a Gordon Research Conference in particularly humorous incident oc New Hampshire, practical jokers by curred at t h e International Congress force of numbers placed the rear of Catalysis in Philadelphia in 1956. axle on a pile of bricks. Eischens, De Boer of the Netherlands ques with characteristic directness, took tioned some of the infrared work by the measure of the situation, placed asking whether some unknown gas a few additional bricks for the de might be chemisorbing on the in scent, and calmly drove the car from frared samples. Eischens quickly- its pedestal. With the car having a replied, " W e have no unknown gases front wheel drive, t h e joke was on the pranksters. in our laboratory."
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Synthesis found for a new class o f boron compounds a t Olin Mathieson
1958
2(C 4 H 9 ) 2 BC1 +
BrMg(CH 2 ) n MgBr
(C 4 H 9 ) 2 B(CH 2 ) n B(C 4 H 9 ) 2
—>-
+ 2MgBrCl
I CH2
\
/
(CH 2 ) n _ 2
B-C4H9 +
(C4H9)3B
CH2
or pentamethylenedimagnesium dibromide. In neither case, however, was the expected reaction product found. Instead, the 1-n-butylboracycloalkanes were isolated. Apparently, says Clark, trie expected α ,ω- ( bis-di-n-butylboryl ) -alkanes are formed and then disproportionated t o give t h e substituted boracycloalkanes. During this work t h e Olin Mathieson researchers also developed a simplified
RESEARCH
synthesis for mixed trialkylboranes. Previously, these have been very difficult to prepare a n d have required many hours of work b y circuitous methods. T h e discovery that alkyl groups will exchange between a Grignard reagent and a trialkylborane gives a much more direct route. Thus, reaction of ethylmagnesium bromide with tri-w-butylborane gave either n-butyldiethylborane or di-n-butylethylborane depending upon the ratio of the reactants and the mode of addition.
Graphite Crucibles Give Pure Potassium Chloride Platinum impurities in p o t a s sium chloride crystals affect their electrical a n d optical properties Use graphite crucibles t o grow really pure potassium chloride crystals; t h e soPhjirsiwl·* called pure crysInorganic tals made in platChemistry ^ inum crucibles are not as pure as many people think. This advice Allen B. Scott of Oregon State College gave to the Division of Physical a n d Inorganic Chemistry. Much interest has centered on t h e alkali halide crystals for studying electrical and optical properties of ionic crystals. Such studies have a bearing on photography, scintillation counters, crystal counters, radiation dosimetry, infrared detection, and the behavior of insulators, to name a few. The alkali halide crystals a r e particularly important because they have simple structures and can b e obtained in large, single crystals. But the properties of KCl crystals are very sensitive to impurities». F o r this reason, the crystals are usually grown in platinum crucibles. However, molten alkali halides attack platinum at high temperatures in t h e presence of air. • Platinum Contamination. Scott and his coworker, William J. Fredericks, of Stanford Research Institute, examined several commercial and laboratory-grown KCl crystals, made, of ACS NATIONAL MEETING
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course, in platinum crucibles. They found tfiat the crystals were luminescent —they emitted yellow light under ultraviolet excitation. Scott and Fredricks then intentionally contaminated potassium chloride with platinum and were able to relate the ultraviolet absorption to platinum content. Their conclusion—contamination in KCl crystals may run as high as 2, p.p.m. (as P t C l 6 - -) and could possibly be more at lower valent forms. T o bypass platinum contamination,
the researchers turned to graphite crucibles. They carefully purified the starting material, used a n inert atmosphere (argon), and avoided contaminating the crucible. T h e result was a KCl crystal which was "pure" as judged by ultraviolet absorption spectroscopy. Next step now that they have "pure" crystals: reinvestigate several important electrical and optical properties of alkali halides. National Science Foundation supported their work.
ACS Award—Paul-Lewis Laboratories Award in Enzyme Chemistry
EUGENE P. KENNEDY At the University of Chicago, Eugene P. Kennedy has a reputation as a n "outstandingly good teacher." Other achievem e n t s , however, lie behind his receipt of the PaulL e w i s Laboratories Award i n Enzyme Chemistry. F o r one thing, Kennedy has been able to tie down t h e specific role of cytidine nucleotides in the enzymatic synthesis of lecithin. H e has pinpointed these nucleotides a s t h e carriers of the ni- Eugene P. Kennedy, University of Chicago trogenous bases, choline (right), looks at his Enzyme Chemistry Award and ethanolamine. Ken- with Richard Kurth of Paul-Lewis Laboratories nedy's^ net synthesis of lecithin lias m a d e it available i n readily measurable amounts and prize for his work on the metabolism has m a d e it possible to follow the of glycerol. stoicfiiometry of lecithin biosynthesis Born in Chicago, Kennedy refrom its building blocks. ceived a B.Sc. from DePaul UniverKennedy also pioneered in demonsity in 1943. Then, with t h e biostrating fatty acid oxidation with chemical division of Armour & Co., isolated mitochondria. His experihe contributed greatly to the World m e n t a l techniques have been used War II program on large-scale fract o synthesize sphingomyelin enzytionation of human blood plasma. matically. This work with sphingoKennedy did his graduate work at myelin may make it possible to study the University of Chicago, at the in vitro the biosynthesis of the comsame time continuing his work with plex lipides found in brain and nerve Armour. He received his P h . D . in tissue. In other investigations, Ken1949, and in 1951 joined Ben May nedy was able to explain the rapid Laboratory for Research and the deturnover of phosphorus in certain partment of biochemistry at the Uniphosphorylation reactions. In 1956, versity of Chicago. H e has been the Soap a n d Glycerine Producers professor of biochemistry since 1956. Association awarded him the glycerol
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