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OCR for page 220
OCR for page 221
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
OCR for page 222
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 pass—the 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.
OCR for page 223
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 C—OEt
1
OEt
ONa
ONa
1 _ 1
2) CH3 C—|OEt + FI |—CH2 CO2 Et > CH3 C—CH2 CO2 Et
1
OEt
OEt
ONa ONa
1 1
3) CHIC—CH—CO2Et~ 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.
OCR for page 225
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 C—OEt + 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
R—C Cl + CH2 = C
OEt
OEt
O O
~ R—C—CH2C—OEt+ 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-
OCR for page 226
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
OCR for page 227
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
OCR for page 228
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 open—but 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
OCR for page 229
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
OCR for page 230
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.
OCR for page 239
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.
OCR for page 240
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.
OCR for page 241
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.
OCR for page 242
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
OCR for page 243
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-
OCR for page 244
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.
OCR for page 247
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.
OCR for page 249
Representative terms from entire chapter:
samuel marion
