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SAMUEL MARION McELVAIN December 9, 1897-Apri! 11, 1973 BY GILBERT STORK S(AMUEL) M(ARION) McELVAIN was for his entire profes- sional career a member of the chemistry department of the University of Wisconsin in Madison. That period spanning the thirty-eight years from his appointment as in- structor in 1923 (full professor from 1933) to his retirement in 1961 coincided with the explosive growth of organic chemistry. That growth resulted in no small measure from a handful of pioneers in a few universities who strove to bring some order to what was then a largely empirical field. McEIvain was one of those pioneers in the formative years of American organic chemistry. His work resulted in major contributions to the understanding of the mechanism of certain base-catalyzed reactions of esters and to the relation between structure and reactivity. It is this latter concern, together with an unusual ability to systematize these relation- ships, that led McEIvain to what was probably his major scientific contribution, the discovery and study of the ketene acetals, a class of substances that proved to be of considerable synthetic interest, as well as of great significance with respect to the emerging theories of chemical reactivity. McEIvain's interest in relating chemical behavior to struc- ture extender! to biological activity, more particularly in the field of anesthesia. This led to another major contribution, 221

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222 BIOGRAPHICAL MEMOIRS the design of local anesthetics, some of which were clevelopecT into important and very successful drugs (Metycaine, Surfacaine) by the pharmaceutical house of Eli Lilly and Company. Solomon and Eliza (Childess) McEIvain had already had five children, four of whom cTied in infancy, when their last, Samuel Marion, was born on December 9, 1897 on a farm near DuQuoin, Illinois. The young McEIvain attended the public school of DuQuoin, graduating from high school in 1915. The family then moved to St. Louis where, urger] by his older brother who was a physician, McEIvain enrolled in the St. Louis College of Pharmacy. Although this foray may have initiated his later interest in the design of possible anesthetics, McEIvain became quickly convinced that his future lay else- where and, in 1916, he became a student in the Department of Chemical Engineering of Washington University in St. Louis. During his undergraduate days there, "Mac," as he had become known, partially supported himself through school by working in a drugstore during whatever spare time he had. Indeed, at the suggestion of the owner of the store, who tract generously offered to pay his expenses if he should be successful, Mac travelect to Columbia, Missouri to take and passthe State Board examination to become a regis- terec] pharmacist. This little excursion did not, however, in- terfere with MacEIvain's chemical career; after his gradua- tion from Washington University in 1920, McEIvain started to work toward his Ph.D. in organic chemistry at the Univer- sity of TIlinois under the tutelage of Roger Adams. In 1923, just three years later, he receiver! his Ph.D. and was ap- pointed instructor in the Chemistry Department of Wiscon- sin. The young instructor wasted no time starting a research program that led him over the years into a number of areas ~ will now discuss. I have organized this brief survey as fol- lows: I. The Acetoacetic Ester Condensation. Il. Ketene Acetals. III. Chemistry of Pyrictines ant! Piperidines.

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SAMUEL MARION McELVAI N I. THE ACETOACETIC ESTER CONDENSATION 223 It may be hard for today's reader to appreciate the rather nebulous approach to chemical mechanisms at the time Mc- EIvain began his research career. One of the then widely held mechanisms for the important CIaisen self-condensation of ethyl acetate (the "acetoacetic ester condensation"), which is shown below, illustrates the situation: O ONa ~ 1 1) CH3 COC2H5 + NaOC2H5 ~ CH.3 COEt 1 OEt ONa ONa 1 _ 1 2) CH3 C|OEt + FI |CH2 CO2 Et > CH3 CCH2 CO2 Et 1 OEt OEt ONa ONa 1 1 3) CHICCHCO2Et~ CHIC= CHCO2 Et+ EtOH 1 1 | OEt H1 . McElvain examined, in a number of papers published between 1929 and 1934, some of the controversies then sur- rounding this reaction. He was able to show, by careful quan- titative experiments: I) that although sodium metal had repeatedly been claimed to be the initiator of the condensa- tion reaction, the initiating reagent is actually the metal alk- oxide formed by various side-reactions of the metal. This suggestion had indeed been put forward very early by CIaisen himself, but it had subsequently been vigorously con- tested, inter alia, by Arthur Michael. 2) That the "acetoacetic ester condensation" could be applied, in contrast to previous claims, to form the ,`3-ketoesters derived from the homologs of propionic esters simply by removal of the alcohol gener- ated in the condensation, thus driving it to completion. 3) That the previous failure to achieve the self-condensation of

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224 B IOGRAPH ICAL MEMOI RS esters such as ethyl isobutyrate, which only have one hydro- gen alpha to the ester carbonyl, is not an intrinsic property of such esters. He concluded that such condensations might succeed if stronger bases than metal alkoxicles were used, ant! his suggestion to Spielman anct Schmidt that these self- condensations might work with mesity~magnesium bromide indeed led to success. Hauser, inclepenclently, made the same observation, using sodium tripheny~methide as the base. These contributions were fundamental to the clevel- opment of our present understanding of base-catalyzed reactions. I I. KETENE ACETALS McEIvain's interest in ketene acetal was originally aroused by a proposal in the literature that I, I-diethoxyethylene, the diethylacetal of ketene, is an intermediate in the above- mentioned CIaisen self-condensation of ethyl acetate. Mc- EIvain's view of the course of the CIaisen condensation was incompatible with this suggestion. The properties ascribed to the supposed ketene aceta] seemed to him highly unlikely, and he showed that the "intermediate" that had been isolated was actually a mixture of ethanol and ethyl acetate! The postulated structure did, however, seem intriguing, and McEIvain set out to synthesize the real ketene acetal. Success was reported in 1936, anct over the next nineteen years McEIvain published thirty-seven papers encompassing the synthesis, properties, and synthetic usefulness of this un- usually reactive class of substances. McEIvain quickly recognized ~1940) that the ketene acetal structure was a special case of what Robert Robinson had labeled a "heteroenoid" system and as such should exhibit especially high nucleophilicity. It is also historically and ped- agogically (more about this later) noteworthy that McEIvain's second and third papers on ketene acetals Id. Am. Chem.

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SAMUEL MARION McELVAIN 225 Soc., 62:964, 1281; 1940) were among the first papers in the United States to make explicit use of the "curved arrows" introduced a few years earlier, largely by Robinson in En- glanct, to indicate the motion of electron pairs attending bond rat . formation. A large number of novel reactions were encountered in the study of ketene acetals for which McEIvain introcluced a general method of synthesis, the dealcoholation of orthoes- ters by means of aluminum alkoxicles. The study of the un- usual chemistry of these nucleophilic species was to lead to a number of surprising reactions, such as the remarkable abil- ity of the parent substance to form carbon-carbon bonds with particularly reactive halides such as benzy! halides. CGH5CH2Br + H2C = Cut O Et TO ~ Cal H5 CH2 CH2 COEt + Et Br OEt This reaction is not of great synthetic utility but has mechanistic analogies with the broact area of enamine chemistry, which was developed much later. Much more potentially useful was the reaction of ketene cliethylacetal with acid chlorides, a reaction that leads to a very simple synthesis of ,l3-ketoesters. This is shown below o RC Cl + CH2 = C OEt OEt O O ~ RCCH2COEt+ EtCI and will serve to illustrate the general type of reaction uncler- gone by ketene acetals with strong electrophiles. Note that the ,`3-ketoester thus formed is accompanied only by the vola- tile ethyl chloride, and that the reaction represents a com- pletely general synthesis of the very class of compounds that had attracted McElvain's early interest in an entirely different context (see above). Every generation is conclemnecl to redis-

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226 BIOGRAPHICAL MEMOIRS cover part of what was known to the previous one, and it is interesting that a very similar reaction has been "introduced" recently that uses a mixed ethoxy trialkyIsiloxy ketene acetal in place of the more convenient ketene acetal. III. PYRIDINE AND PIPERIDINE CHEMISTRY McEIvain's early interest in pharmacology focused on co- caine analogs during his graduate work with Roger Aciams at Illinois. By the time he started independent work as an in- structor at Wisconsin, McEIvain was convinced that struc- tures embodying relatively simple elements of the cocaine structure might show both enhancer] anesthetic activity and lowered side effects. McEIvain's first independent publica- tion (1924) describes the synthesis of benzoates of simple N-hy(lroxyalky~pipericlines. It is extraordinary that it in- cludes the substance that eventually became, after its intro- duction by Eli Lilly, the widely used local anesthetic Mety- caineTM. This marked the beginning of a long and fruitful association between McEIvain and Eli Lilly. A number of additional substances of this general type were synthesized in collaboration with Thomas P. Carney, who was a postcloctoral associate of McEIvain's in 1943 and 1944 anal later became a vice president of Eli Lilly. ~ still remember the sight on Tom Carney's laboratory bench when all of the various piperidine hyctrobromides he hac! made on one of his last days at work were stacked to dry on pieces of filter paper held on ring stands all over the laboratory. One of these substances eventually was developed by Eli Lilly as the clinically valuable local anesthetic Surfacaine. Although he returned to this pharmaceutical interest in anesthetics from time to time, McEIvain mostly used it to spark important funclamental research both in piperidine and in pyridine chemistry. This area, like that of ketene acetal chemistry, remained a lifelong interest that found

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SAMUEL MARION McELVAIN 227 expression in over thirty papers. In pyridine chemistry, McEIvain made important studies of the bromination and sulfonation of pyridines and introduced a number of much- improved methods for the synthesis of several of these heteroatom-substituted pyriclines. He was the first to find a general synthesis of 3- ant! 4-pipericlones by the use of the Dieckman cyclization of aminoctiesters. In many cases the resulting ketones were further elaborated to potential co- caine analogs. McEIvain's involvement in piperidine chemistry, paren- thetically, turned out to be of considerable interest to me: it led to my going to the University of Wisconsin for the Ph.D. because of the (correct) surmise that McEIvain might show some sympathetic interest in my planned use of 4-piperi- dones in a quinine synthesis. McELVAIN AS TEACH ER Important as many of McEIvain's scientific contributions have proven to be, his influence as a guide of the young people who elected to work with him for the doctorate was even greater and this influence dicI not confine itself to the members of his group. McEIvain was an outstanding teacher, and his graduate courses were extremely successful. One was the celebrated course in qualitative organic analysis for which he wrote a successful text The Characterization of Organic Com- pounds (1945; revised edition, 19531. Many first tasted in that course the thrill of discovery and acquirer! the skill of putting together the pieces of a chemical detective story, of weighing the importance of conflicting clues, and of exercising their powers of logical analysis. This, of course, was all without benefit of NMR or of infrared spectroscopy and without the help of gas, liquid, or thin layer chromatography! The course relied sometimes, as any course must have at the time, on color tests of dubious generality and macie use of samples of

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228 BIOGRAPHICAL MEMOIRS "unknowns" that were very large by current standards. Much was learned in the course, in large part because of McEIvain's insistence on clear, logical analysis. In one other graduate course, or rather a portion of a graduate course that he shared with two other members of the organic staff, McEIvain must have been one of the first to teach systematically the particular way to Took at reactivity that was then called the "Electronic Theory of the English School." This referrer! to the analysis of the course of re- actions based on an attempt at the rational prediction of the fate of electron pairs involvecl in bond making and breaking. The brilliant systematization Robinson had clevelopecT in an Outline of an Electrochemical (ElectronicJ Theory of Organic Re- actions (1932) had been given wider circulation by the chap- ter written by I. R. Johnson in the first edition (1938) of Gilman's celebratecl Advanced Organic Chemistry. This ap- proach to chemistry was, however, far from common when McEIvain started teaching it formally. McEIvain was able to project a certain avuncular sternness (everyone in his group referred to him as "Uncle Mach. He was always accessible, his cloor openbut one had to have something to say. One clip not drop in for casual conversa- tion. Mac wouict usually be working at his desk on a manu- script that he would later turn over to Grace Legler, the organic group's secretary. He would raise one eye from his writing toward the visitor, who was expected to get to the point, unassisted. Having thus ensured that he would be spared trivialities, Mac then gave the matter his concentrated attention. Perhaps his sense of humor was even more appre- ciated because of this kincT of aloofness. ~ will always re- member the sullen hearty laughter with which he greeted an outraged report of my (presumecI?) lack of cooperation in enforcing rigorous discipline on the undergracluates in the laboratory section in which ~ was a teaching assistant. He then

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SAMUEL MARION McELVAIN 229 arranges! for me to get a University Fellowship to replace the assistantship for which the powers that be had found me no longer acceptable. It took some time for the graduate students in Mac's group to appreciate the warmth behind the projected aloof- ness. It became quite evident when Professor and Mrs. Mc- EIvain entertained those of his group who tract remained in Madison at Thanksgiving dinners in their home. And it was with great anticipation that, on several such occasions, we walked through the snow to the house on 2017 Adams Street. One cannot help thinking that McEIvain's special ability to instill high standards and respect for hard work, his emphasis on developing responsible self-reliance, at the same time that he was able to make his students aware of his genuine interest in their problems, were responsible for the remarkable fact that three of the students who receiver! their doctorates in his group eventually won the American Chemical Society Award in Pure Chemistry. No other teacher of organic chemistry has yet equalled this record. Professor McEIvain was married in 1926 to Helen Roth of Madison. They had two daughters, Anne, who is now Mrs. William R. Frazier of Princeton, N.~., and lane, now Mrs. Car! E. Jenkins of Bath, Ohio. ~ have had the good fortune to know Mrs. McEIvain for many years. The cheerful enthusi- asm, which ~ first encountered at the Thanksgiving parties ~ mentioned, was just as apparent when I had the honor of being McEIvain Visiting Scholar in Madison in 1977. It would seem appropriate to encI this brief account of Professor McElvain's career by recording some of the more notable recognitions accorcled him: he was chairman of the Organic Division of the American Chemical Society in 1945 and 1946; on the editorial board of the Journal of the American Chemical Society, 194~1956; and he was elected to the Na- tional Academy of Sciences in 1949. The Regents of the

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230 BIOGRAPHICAL MEMOIRS . University of Wisconsin awarded him the title of Professor Emeritus when he retired early (at the age of sixty-three) in 1961. The University of Wisconsin has recognized his leader- ship, which contributed so much to bringing its Chemistry Department to the front rank, his scientific accomplishments, and his loyalty to the University in a variety of ways. An Organic Symposium was held in his honor, in Madison, upon his retirement in 1961. The S. M. McEIvain Professorship was created in 1972 (with Harlan Goering as its first incumbent). The S. M. McEIvain Visiting Scholarship was established in 1977 and, finally, the organic laboratories in the Daniels- Matthews Chemistry Building at Wisconsin were named the Samuel M. McEIvain Laboratories of Organic Chemistry at a ceremony on March 15, 1979. A great honor befitting an outstanding man. ~ WISH TO EXPRESS my sincere thanks first to Mrs. McElvain, whose recent death before this could be published was a source of sadness to many, and also to professors Aaron i. Ihde and Harlan Goering who supplied me with much essential material.

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SAMUEL MARION McELVAIN 239 diethylacetal with various halogen compounds and acids. }. Am. Chem. Soc., 64:254-59. With Harry Cohen. Ketene acetals. VIII. The reaction of ketene diethylacetal with a, ,8-unsaturated carbonyl compounds. I. Am. Chem. Soc., 64:260-65. With P. M. Walters. Ketene acetals. IX. Ketene dialkylacetals. I. Am. Chem. Soc., 64: 1059-60. With l. Walter Nelson. Preparation of orthoesters. I. Am. Chem. Soc., 64:1825-27. With Philip M. Walters. Preparation and properties of certain polyethoxyethanes and their bromo derivatives. I. Am. Chem. Soc., 64:1963-65. With Howard Burkett. ~ 1-Alkoxyvinyl)- and ~ 1-Alkoxyethyl)- barbituric acids. }. Am. Chem. Soc., 64:1831-36. With Robert L. Clarke and Griffin D. Jones. Ketene acetals. X. The elimination of hydrogen bromide from the acetals of c~-bromoaldehydes. Isopropyl- and n-propylketene diethyl- acetals. I. Am. Chem. Soc., 64:1966-69. With Philip M. Walters and Robert D. Bright. Constituents of the volatile oil of catnip. II. The neutral components. Nepetalic anhydride. }. Am. Chem. Soc., 64:1828-31. With Harrison I. Anthes and Sydney H. Shapiro. Ketene acetal. XI. The pyrolysis of ketene acetals and orthoesters. I. Ant. Chem. Soc., 64:2525-31. 1943 With M. A. Goese. 5-Ethyl-5-~2-pyridyl)-barbituric acid. I. Am. Chem. Soc., 65:2226-27. With M. A. Goese. Halogenation of pyridine. I. Am. Chem. Soc., 65:2227-33. With M. A. Goese. Sulfonation of pyridine and picolines. J. Am. Chem. Soc., 65:2233-36. With A. Jelinek. Ketene acetals. XII. Reaction of ketene diethyl- acetal with diazonium salts. }. Am. Chem. Soc., 65:2236-39. With }. W. Langston. Ketene acetals. XIII. Cyclic trimerization of ketene diethylacetal by hydrogen fluoride: 1,1,3,3,5,5,- hexaethoxycyclohexane. }. Am. Chem. Soc., 65:2239 41. With D. Kundiger. Bromoacetal. Org. Synth. 23:8-10. With K. H. Weber. Ethyl benzoylacetate. Org. Synth. 23:35-36. With Robert E. Kent.,l3-Methylglutaric acid. Org. Synth., 23:60-62.

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240 BIOGRAPHICAL MEMOIRS 1944 With E. L. Engelhardt. Ketene acetals. XIV. Reactions of ketene acetal with quinones. }. Am. Chem. Soc., 66:1077-83. With I. W. Langston. Polymerization of cyclohexene with hydrogen flouride. }. Am. Chem. Soc., 66:175~64. 1945 With Bryce E. Tate. Nitrogen analogs of the ketene acetals. }. Am. Chem. Soc., 67:202-4. With Bernardo Fajardo-Pinzon. Ketene acetals. XV. Ketene di- phenylacetal and triphenylorthoacetate. J. Am. Chem. Soc., 67:650-53. With Bernardo Fajardo-Pinzon. The preparation and alcoholysis of phenyl iminoester hydrochlorides. J. Am. Chem. Soc., 67: 690-91. With Arthur Jelinek and Kurt Rorig. Ethane-,l- and propane-1,3- disulfonic acids and anhydrides. J. Am. Chem. Soc., 67: 1578-81. 1946 With Gilbert Stork. Piperidine derivatives. XV. The preparation of 1-benzoyl-3-carbethoxy-4-piperidone. A synthesis of guvacine. I. Am. Chem. Soc., 68:1049-53. With Gilbert Stork. Piperidine derivatives. XVI. C-Alkylation of 1-benzoyl-3-carbethoxy-4-piperidone. Synthesis of ethyl 3- ethyl-4-piperidylacetate (dl-ethyl cincholoiponate). J. Am. Chem. Soc., 68:1053-57. With Calvin Stevens. Ketene acetals. XVI. Phenylketene diethyl- and dimethylacetals from the pyrolsis of the corresponding orthoesters. I. Am. Chem. Soc., 68:1917-21. With R. E. Kent and Calvin Stevens. Ketene acetals. XVII. The alkylation and acylation of substituted ketene acetals. I. Am. Chem. Soc., 68:1922-25. With Thomas P. Carney. Piperidine derivatives. XVII. Local anesthetics derived from substituted piperidinoalcohols. }. Am. Chem. Soc., 68:2592-2600.

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SAMUEL MARION McELVAIN 1947 241 With Gilbert Stork. Preparation of ethyl ,8-benzylaminopropionate and benzyl-di(,8-carbethoxylethyl)-amine. i. Am. Chem. Soc., 69:971-72. With Robert L. Clarke. The preparation, alcoholysis and reduction of cyanoacetaldehyde diethylacetal. Malonaldehyde tetraethyl- acetal. l. Am. Chem. Soc., 69:2657-60. With Calvin L. Stevens, Ester and orthoester formation in the alcoholysis of iminoester hydrochlorides. A proposed mech- anism. T. Am. Chem. Soc., 69:2663-66. With Robert L. Clarke. Ketene acetals. XVIII. Pentaethoxyethane and tetraethoxyethylene (diethoxyketene diethylacetal). J. Am. Chem. Soc., 69:2661-63. With L. A. Perez-Medina and R. P. Mariella. The preparation and reactions of some polysubstituted ovridines. 2-MetEvl- 3 - hydroxy- 5 - hydroxymethylpyridine 1 ~ __ (4 - deshydroxymethyl- pyridoxin). I. Am. Chem. Soc., 69:2574-79. With Calvin L. Stevens. A study of new approaches to c~-halo- genated orthoesters. J. Am. Chem. Soc., 69:2667-70. 1948 With C. L. Rose, T. P. Carney, and K. K. Chen. New piperidine derivatives as local anesthetics. Anesthesiology, 9:373-80. With M. I. Curry. Ketene acetals. XIX.2-Methylene-1,3-dioxolanes and 1,3-dioxanes. i. Am. Chem. Soc., 70:3781-86. With Kurt Rorig. Piperidine derivatives. XVIII. The condensation of aromatic aldehydes with 1-methyl-4-piperidone. }. Am. Chem. Soc., 70:182~25. With Kurt Rorig. Piperidine derivatives. XIX. Esters of substituted 4-piperidinols. J. Am. Chem. Soc., 70: 1826-28. 1949 With J. P. Schroeder. Orthoesters and related compounds from malono- and succinonitriles. I. Am. Chem. Soc., 71:4(~46. With J. P. Schroeder. Ketene acetals. XX. The preparation and properties of cyanoketene acetals. Some novel benzylation re- actions. I. Am. Chem. Soc., 71:47-53.

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242 BIOGRAPHICAL MEMOIRS With E. H. Pryde. 2,2,5,5-Tetramethylpiperazine and derivatives. I. Am. Chem. Soc., 71:32~31. With John F. Vozza. Piperidine derivatives. XX. The preparation and reactions of 1-methyl-3-piperidone. }. Am. Chem. Soc., 71:89~900. With Robert E. McMahon. Piperidine derivatives. XXI. 4-Piperi- done, 4-piperidinol and certain of their derivatives. l. Am. Chem. Soc., 71:901-6. The ketene acetals. Chem. Rev., 45 :453-92. 1950 With R. E. Lyle, fir. Piperidine derivatives. XXII. Condensation of 1-methyl-4-piperidone with active methyl compounds. I. Am. Chem. Soc., 72:384-89. With I. C. Safransky, Jr. Piperidine derivatives. XXIII. 1-methyl- 4-phenylpiperidines and related compounds. I. Am. Chem. Soc., 72:3134-38. With I. T. Venerable. Ketene acetals. XXI. Dealcoholation of orthoesters- dimethylketene dimethylacetal. J. Am. Chem. Soc., 72:1661-69. With }- C. Safransky, Jr. Bromo derivatives of 1-methyl-3- carbethoxy-4-piperidone. J. Am. Chem. Soc., 72:3295. 1951 With Leo R. Morris. Ketene acetals. XXII. Diethoxymethylketene dimethyl acetal. I. Am. Chem. Soc., 73:20~7. With Paul M. Laughton. Piperidine derivatives. XXIV. 1-methyl-4-phenyl-3-piperidone and related products. I. Am. Chem. Soc., 73:448-52. With Wm. R. Davie. Ketene acetals. XXIII. Dealcoholation of orthoesters with aluminum tert-butoxide. I. Am. Chem. Soc., 73: 140~1402. With A. N. Bolstad. Ketene acetals. XXIV. Preparation and proper- ties of ketene divinyl acetal and related compounds. l. Am. Chem. Soc., 73:1988-92. With Bryce E. Tate. The thermal decomposition of iminoester salts and the cleavage of orthoesters by these salts. I. Am. Chem. Soc. . 73:2233-38. With Bryce E. Tate. The alcoholysis of diethyl diiminomalonate

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SAMUEL MARION McELVAIN 243 monohydrochloride. Some new pyrimidines. J. Am. Chem. Soc., 73:276~64. With Stanley B. Mirviss and Calvin L. Stevens. Ketene acetals. XXV. Diphenylketene dimethyl acetal. l. Am. Chem. Soc., 73: 3807-11. With Melvin M. Olson. Base-induced reactions of certain benzyl esters. I. Am. Chem. Soc., 73:482~27. 1952 With Henry l. Schneider and Homer Adkins. The hydrogenation of amides and ammonium salts. The transalkylation of tertiary amines. I. Am. Chem. Soc., 74:4287-90. With Richard D. Mullineaux. Ketene acetals. XXVI. The prepara- tion and properties of some w-cyanoalkylketene acetals. l. Am. Chem. Soc., 74:1811-16. With Wm. R. Davie. Ketene acetals. XXVII. The bromination of various ketene acetals. J. Am. Chem. Soc., 74:181~21. With Leo R. Morris. Ketene acetals. XXVIII. The dehalogenation of a, a-dibromoacetals. Isopropenylketene diethylacetral. I. Am. Chem. Soc., 74:2657-62. With Herbert F. McShane, fir. Ketene acetals. XXIX. Mechanism of the reaction of ketene acetal with various halides. I. Am. Chem. Soc., 74:2662-67. 1953 With Charles H. Stammer. Some reactions of 1,2-diethoxyethylene and its bromo derivative. I. Am. Chem. Soc., 75:2154-58. With Clyde L. Aldridge. Ketene acetals. XXX. Alkylation of di- methylketene dimethylacetal. I. Am. Chem. Soc., 75:3987-93. With Clyde L. Aldridge. Ketene acetals. XXXI. Dimethylketene ethyleneacetal. J. Am. Chem. Soc., 75:3993-96. 1954 With E. I. Eisenbraun and B. F. Aycock. Some observations on the C-methyl determination. I. Am. Chem. Soc., 76:607-9. With Loren W. Bannister. 1,4-Diazabicyclo t2.2.2] octanes and 1,5-diazabicyclo t3.2.2.] nonanes from piperazines and homopi- perazines. J. Am. Chem. Soc., 76:112~37. With William B. Dickinson and Robert I. Athey. Piperidine deriva-

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244 BIOGRAPHICAL MEMOIRS fives. XXV. The reaction of certain 3-substituted 1-methyl- 4-piperidones with organometallic compounds. J. Am. Chem. Soc., 76:5625-33. With Edward R. Degginger and John D. Behn. Ketene acetals. XXXII. The condensation of ketene dimethyl acetal with various aldehydes and ketones. l. Am. Chem. Soc., 76:5736-39. 1955 With P. Harold Parker, Jr. Piperidine derivatives. XXVI. merhvl-3-benzylidene-4-piperidone dimer. I. Am. Chem. Soc., 77:492-93. With E. I. Eisenbraun. The constituents of the volatile oil of catnip. III. The structure of nepetalic acid and related compounds. I. Am. Chem. Soc., 77:1599-605. With Richard S. Berger. Piperidine derivatives. XXVII. The con- densation of 4-piperidones and piperidinols with phenols. J. Am. Chem. Soc., 77:2848-50. With E. J. Eisenbraun. Configuration of 3-methylcyclopentanones and related compounds. I. Am. Chem. Soc., 77:3383-84. With W. L. McLeish. Ketene acetals. XXXIII. The addition of halogens and cyanogen compounds to methyl ketene diethyl acetal. I. Am. Chem. Soc., 77:3786-89. With R. E. Statur, fir. Ketene acetals. XXXIV. Tetra- and penta- methylene ketene acetals. I. Am. Chem. Soc., 77:4571-77. With G. Robert McKay, Jr. Ketene acetals. XXXV. Cyclic ketene acetals and orthoesters from 2,2-dimethoxy-2,3-dihydropyran. }.Am.Chem.Soc., 77:5601-6. 1956 With Martin D. Barnett. Piperidine derivatives. XXVIII. 1-Methyl- 3-alkyl-4-phenyl-4-acyloxypiperidines. J. Am. Chem. Soc., 78:3140-43. With P. Harold Parker, Jr. Piperidine derivatives. XXIX. Octa- and decabydroisoquinolines from 1-methyl-3-carbethoxy-4-piperi- done. J. Am. Chem. Soc., 78:5312-14. With G. Robert McKay, Jr. Ketene acetals. XXXVI. The prepara- tion and properties of acylketene acetals. J. Am. Chem. Soc., 78:6086-91.

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SAMUEL MARION McELVAIN 245 1957 With E. }. Eisenbraun. Interconversion of nepetalic acid and isoiri- domyrmecin (Iridolactone). I. Org. Chem., 22:97~77. 1958 With David H. Clemens. Piperidine derivatives. XXX. Dialkyl-4-arylpiperidines. }. Am. Chem. Soc., 80:3915-23. 1959 With David H. Clemens. Ethyl (l-phenylethylidene) cyanoacetate. Org. Synth., 39:25-26. With David H. Clemens. ,8-Methyl-,8-phenylglutaric acid. Org. Synth. 39:54~55. With Philip L. Weyna. Ketene acetals. XXXVII. Cyclopropanone acetals from ketene acetals and carbenes. I. Am. Chem. Soc., 81 :2579-88. With Rodney B. Clampitt. The reaction of 2-substituted cyclo- hexanones with organometallic compounds. }. Am. Chem. Soc., 81 :559~98. 1960 With Thomas A. Lies .2,2,5,5-Tetramethyl- 1,4-diazabicyclo ~ 2.2.2.] octane methochloride. I Am. Chem. Soc., 82: 16~69. With David C. Remy. Piperidine derivatives. XXXI. Certain 6-oxooctahydro- and decahydroisoquinolines and related com- pounds. I. Am. Chem. Soc., 82:396~66. With David C. Remy. Piperidine derivatives. XXXII. Reaction of 1-acyl-4-piperidones with organometallic compounds. I. Am. Chem. Soc., 82:396~70. BOOKS 1925 With Homer Adkins. Practice of Organic Chemistry in the Laboratory. New York: McGraw-Hill Book Co. 1928 With Homer Adkins. Elementary Organic Chemistry. New York: McGraw-Hill Book Co.

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246 BIOGRAPHICAL MEMOIRS 1933 With Homer Adkins. An Introduction to the Practice of Organic Chemistry in the Laboratory, 2d ed. rev. New York: McGraw-Hill Book Co. 1940 With Homer Adkins and M. W. Klein. An Introduction to the Practice of Organic Chemistry in the Laboratory, 3d ed. New York: McGraw- Hill Book Co. 1945 The Characterization of Organic Compounds. New York: The Mac- millan Co. 1953 The Characterization of Organic Compounds, rev. ed. New York: The Macmillan Co.

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SAMUEL MARION McELVAIN PATENTS 1929 U.S. Patent 1,714,180 (May 21, 1929). Piperidine Derivatives. 247 1930 U.S. Patent 1,784,903 (Dec. 16, 1930~. Piperidine Derivatives (local anesthetics). 1935 U.S. Patent 1,997,828 (April 16, 1935~. Piperidine Derivatives. 1946 U.S. Patent 2,394,195 (Feb. 5, 1946~. With Howard Burkett. Bar- bituric Compounds. 1947 U.S. Patent 2,415,897 (April 15, 1947~. With Howard Burkett. Bar- bituric Compounds. 1947 U.S. Patent 2,418,977 (April 15, 1947~. With Melvin A. Goese. Production of Bromopyridines. 1948 U.S. Patent 2,439,818 (April 20, 1948~. With Thomas P. Carney. Substituted Esters of Benzoic Acid. U.S. Patent 2,448,996 (Sept. 7, 1948~. With Thomas P. Carney. 3-~2' Methylpiperidino)-propyl p-n-Butoxybenzoate and Acid Addition Salts Thereof. U.S. Patent 2,448,997 (Sept. 7, 1948~. With Thomas P. Carney. Piperidine Propanol Esters of Phenylacetic Acid. U.S. Patent 2,448,998 (Sept. 7, 1948~. With Thomas P. Carney. 3-~2',6'-Dimethylpiperidino)-propyl Salicylate and Acid Salts Thereof. 1949 U.S. Patent 2,463,989 (March 8, 1949~. With Gilbert Stork. The Preparation of Acylated Aminoesters.

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248 BIOGRAPHICAL MEMOIRS 1959 U.S. Patent 2,892,842 (June 30, 1959). 4-(m-Hydroxyphenyl) Piperidines. 1960 British Patent 853,814 (Nov. 9, 1960). Piperidine Compounds.

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