Dennis P. Ryan Yale University New Haven. Connecticut 06520
Outline of a Course in the History of Organic Chemistry
Early in 1976, it became apparent that the bicentennial celebrations in the United States could be used as a convenient excuse for a large number of historical activities during the year. Surely, there was no more convenient time for a semester course in the historv of oreanic chemistrv. Given the lack of opportunity in the'average undergradu&eFs schedule, the unfavorable attitude towards teachina the historv of science to students of science on the part of some (I, 2 ) , and the lack of popularitv indicated bv the scarcity. of .good texts (at least . . in Ktiglish~,it almost st!enied a case of now or newr! Acc(~rdinclv, imder the a~apicesufth? Yale (:dlt.oeSeminar Propam ofYale ~ n i v e r s i t y , a nundergraduate seminar in the history of organic chemistry was offered in the fall of 1976. he purposes of this course were to lead the students to the original literature of organic chemistry, to fit the parts of this science into a coherent whole, to examine the process of creativity as seen in famous chemists, to give the student an appreciation for the mechanisms by which theories are born and discarded, and to display some of the more prominent effects of organic chemistry on the progress of human history. The objective was to delve, not so much into the data on which the science is based, hut into its structure, its cumulative Dower, its dependence on technology and on other sciences, a i d the human side of the discoveries that have led to its successes. The background of the students demonstrated the wide appeal such a course can have: chemistry majors, philosophy majors, history of science majors, and biochemistry majors were represented. The single prerequisite was a year's course in nreanic chemistrv. Since credit for the course could not he applied to any of the standard undergraduate majors, enrollment was small. but this allowed a more informal atmosphere and individual attention. Readings were taken from the original literature as much as possible. A collection of early articles in translation was used as a text (3). A term paper. . . oral presentation. and a final exsmtnatwn that asktd h r a criticnl evaluation nf a current issue of the Jorrrnrrl of t h .\nwricon ~ I'hwniral S o r i v l ~frum n historical perspective were required of each student. Term paper topics included: "Vitalism," "A History of Carbenes," "Ladenberg-Benzene," and a biography of Sir Derek Barton. Responses to the course from the students were quite favorable and the instructor had the time of his life. Of special help in preparation for the course was a letter of Stanislao Cannizzaro, reprinted recently under the title, "Sketch of a Course in Chemical Philosophy" ( 4 ) .The standard histories of Ad. Wurtz (5),Henrich ( 6 ) ,and Schorlemmer (7) were useful sources for the 19th century. Fewer secondary sources for the 20th century are available. Also, it was not thought desirable to overlap extensively with the content of other nurues in the regular curriculum. Forlunately, however, ~t i> common for a first year course in organic chemistry to fnlluw the outline of a hulkv intnxlucrory text hut to fail to cover all the topics for lack of time. An op$onal chapter or two of biochemical relevance are usually included, but often omitted are several topics of considerable historical interest. Accordingly, it was possible to look into industrial organic chemistry, medicinal chemistry, the chemistry of the dye industry, organic polymer chemistry, and their impact on the history of the 20th century without competition with courses that emphasize learning the art of synthesis and the concept of mechanism. ~
~
U~
Moreover, we were able to take more time than is usually done to look a t the historical context of some items of current theoretical interest. For example, the Woodward-Hoffmann rules of orbital symmetry take on new interest when viewed in the context of the discoverv of asvmmetrv bv Van't Hoff and Le Bel. The controversy over the &isten& okon-classical ions is easilv connected with the discoverv of the tetravalence of carbon in the 1850's. Another general theme for the course was found in the perennin1 rearch by i~ryanicchemists for the solution tu thr r~rohlemof their st:icnce. While solving small prohlems is ;In intrinsic part of every course in organic chemistry and is the substance of the practice of the science, it is often forgotten that the science as a whole represents a larger problem that has been attacked with varying degrees of success. For exnmple, the discowry that cer& compositims of matter cuukl remnin invariant during chemical reactimx was thv hnais ot' the theorv d r a d i r a l s set forth bv I.it.hie and 1)umas i n the early 1836's. The power of this "concepi led them to state (8) To produce with three or four elements combinations as varied as and perhaps morevaried than those which form the mineral kingfor dom. nature has taken acourse as simole as it was unexoected: . nit11 the elementi *he hi mil& compnunds uhwh manilcsl all thr In ~~ ~(hat. c ~s i w a r e pruprrtlesof e l ~ m e ~ ~ t a r y s ~I ~~ l ~~ ~~ t P~ And convinced, is the wholesecret o f organic chemistry. ...In mineral chemistry the radicals are simple; in organic chemistry the radicals are compound; that is all the difference.
.~ ~
~
~~~~
638 / Journal of Chemical Education
The discoverv that the internal relationshi~sof atoms in radicals could be explained in terms of the tetravalence of carbon and its capacitv to combine with itself was made independently I,).~;.kuleandArchibald Scott Couper in the lat$, 1950's. Cuuper s t a t e 4 "These two rmmerties suffice, in my opinion, to explain all that is presented as characteristic h i organic chemistry" (9).The extension of these concepts into space by Van't Hoff and Le Be1 in the 1870's was another milestone. Wislicenus looked back years later and said The doctrine of atomic arrangement in three dimensions is a logical and necessary stage,perhaps the final stage, in the chemical theory of atoms (10). On the other hand, there have not t~cenlacking those whosee organicchemistry as a practical tool apart from a theoretical base. ('laisen and Rruntny, two assistants of Adolf van Baeyer, rvported that onrc he rushed into the lahoratorv with hi* rigar unlit, solemnly raised his hat twice, and l~roslaimedi l l , I hwc lust w r d f r m End Ficher that he ha. bmvghr G~=ntlcmcn! off rhr r mnplrrc s,nrhe,i, c,f glucosc. This hrrnlds i h r rnd r i r y a n , ~ . c h t m , . ; r r \ !1.~1'siinivh utt the terprne5. and cnly the sllmrs will he left!
iinr have such aspirations vanished during the present centurv. M. .I. 3. Dewar has cornmenred on the success of iemiempirical quantum mwhanical calc~tlationsof conjugated n systrms and the ~~ossihilit). of extmding surcrssfully such a treatment to n bonds as well. If it were possible to do so, he concludes that (12,:"We w d d haven complelesulurion of the hasir prohlems of chemistry." (All italics above are mine.)
Topics Covered I ) TheLi,ora,llre,lfor~snicCholnislry 1141 Pnracelius. latmrhemislry, and the"W"ld- ofCreafiun 1151 Ramirl Phihniohv. Lihaviur and the First Textbonk 0 5 1
Acknowledgment
The author gratefully acknowledges the support of the colleee seminar committees of Savbrook and Timothv Dwieht C'oll&es of Yale L'niversity. H e also indebted to dr. J. ~ i chnel MrRride. Rorer Mncklis. John Kaufman. David Plarhe. and Stephen ~ a s s & n a n for helpful discussi&
-
Literature Cited IrLz. L I , RasieBmkr h e . . New York, 1966. 151 Wurh. Ad.. "A History of Chemical Theory from the Age of Lavuisier to the Present Time." Macmillan and Co.. London. 1869. I61 Henrich, F. A. K.,"Theorier of OlganicChemi~ry."John Wileyand Lms. h e . , New York. 1922. 17) Schorlemmer, C.,"The Rise and Development of Owaganic Chemistry: Macmillan and Cu.. London. 1891. (81 Liebip, L a n d Oumar, J. B..Compt. r m d u s . 5,567 11837). 19) Cnuper.A.S.. Compl. rendus, 16.1157 118581. (101 Wislicenus, J.. Preface to the 2nd edition of Van? Hofrs"Die I h m r u n l ' d e r Atsmr im Roume." Braunschweig, 1894, p. VII-VIII. 111) Bawer. A,, quoted in Read. .I.. "Humour and Humanism in Chemi~trv." G. Bell. ~ b " d ~ n1.9 1 7 , ~ 258-9. . (121 Dewar. M. J. S . J . sr. C h e m S o r . 89,3089 11967). 1131 Reeommendation~oflheACSNiifhBiiiiiilFduc,.l.CHEM.EDUC., 53.672 (19761. (141 Chaucer.G.."TheChanunrYemsnne~Tale." 1151 Hannaway, 0,"TheChemisfs and the Word." J a h n r Hapkins University Press, Bartimore. 1975. 1161 F ~ u n d I., . "The Study uf Chemical Composition." Dover Publications. Inc.. New Yurk. 1968. I n 1 Wohler.F..Annokn drrPhyrik undChemie. 88.253 (18281. 118) Rm0ke.J. H . , A m h u 15,84 (1968). 1191 CusLa. A. R.. "M. E.Chwreul: Pioneer uf0rganie ChemiLry."State Hirturieal S d e t y of Wisconsin. Madison, Wisconsin. 1962. 1201 Wohler. F.. and Liehia. J.. A n n a k n der Phormarie, 3. 249 l18RYl. Lmnsiatim in rep erenee (3). (211 Wind1er.S. C. H..Ann.. 33.30611840). I221 Laurent. A.. method^ d e Chimie," Mallet~Bsehelier. Paris. 1854. pp. 218-251. trsnrlatiun in reference 131. (231 Wil1iamsnn.A. W., J . C h s m Soc.. 4,350 118521. 1241 Frankland. 8..Pfiii. Tmna.Roy.Soc, ilnndonl, ld2.417!18521. (251 Kekule. A..Ann, 106,129 118581. 1261 Rykou.G. V., J. CHEM.EOUC.. 39.220 119621. 1271 Van't Hoff. J. H.. Archices Neerlondois~rder Svieneer ILracl?sel Nnlurelkr, 9.445 118741. tmnsiatiun in reference 131. 1281 la BeI. J.A.. Ruf1 Sor. Chim.. 22.:1:37 118741,transistiun in reference (31. 1291 Willrtatter, R.,"Fmm My Life," W.A. Benjamin Inc..Ner Yoik. l9651Guran M.,"The Storyof Fritz Hsber." U ~ i i v e r ~ i t y o f o k l a h o mPress. a Norman. Oklahoma. 1967. 1301 Tedder, d. M.. Nechvatel, A . and Jubb. A. H., "Industrial l'nrducrr."John \file? & Ssnr. New York. 1975. I311 Flury. P. J., "Principles of Polymer Chemistry: C m e l l University Press. Ithaca. New York. 1953.eh. 1. 1321 Poynter. F. N. L.. "Chemistry in the Serviceclf Medicine."Pitman Medical Puhlirhinp Cn.. Ltd., London, 1963; Hansch, C.. J.CHEM. EDUC.. 51,960 119741. 1331 Gumberg, M . J . A m m Chem Sor 22,757 119001; McRride..l. M.. Tetrohpdnm. 30,
.
1958. 1351 Ryk0u.G. V.. Ch?rnia. 10,199 11966). 1361 Graham. L. R., Ilia, 55, 20 (I9641. 1371 Wmdwaid,R. & a n d Horfmann.R..Arcounlr Cham. Re*.. I. 17 119681; Zimmermnn. H. E.. Arrounir C h e m Rrr., 4, ?7? 1197ll;Rarsun. J . A,. Arrounlr C h e m R e h . 5. lrVii19771 .. .,.. .,.
(381 Eliol, E. L..d.CHEM. EDUC.,52,762 119751, (391 Brown. H. C.. Trirahrdron. 32. 179 119761: Olah. G..Accounts Chem Re,?., 9, 41 ,>n,
