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OCR for page 330
OCR for page 331
ARTHUR MICHAEL
August 2, 1853-February 8,1942
BY LOUIS F. FIESER
THE FOLLOWING MINUTES were placed upon the records of
the Faculty of Arts and Sciences of Harvard University at
the meeting of May 18, 1943.~
"Arthur Michael, Professor of Organic Chemistry, Emeritus,
died on February 8, 1942, in Orlando, Florida, in the eighty-
ninth year of his age. Michael was born in Buffalo, New York,
on August 7, 1853, the son of John and Clara (Pinner) Michael.
He attended the Briggs Classical School in Buffalo. No formal
classes in chemistry were held there at that time but Michael
had special instruction in this subject at school from one of his
teachers, and he performed the experiments by himself with
great enthusiasm in a laboratory which his father had fitted up
for him at home.
"Thereafter, Michael had planned to go to Harvard College,
but a serious illness intervened. As a result the Michael family,
in the summer of 1871, went for a long sojourn in Europe. They
arrived in Berlin just in time to see the German Army, fresh
from the Siege of Paris, march triumphantly down Unter den
Lind en.
"After he had recovered from his illness and after an in-
terval of preoccupation with art and literature, Michael suc-
~ E. W. Forbes, L. F. Fieser, and A. B. Lamb, "Arthur Michael," Harvard
University Gazette 38(1943):246.
331
OCR for page 332
332
BIOGRAPHICAL MEMOIRS
ceeded, in spite of his meager chemical training, in gaining
admission to the Chemical Laboratory of Professor Hofmann
at the University of Berlin. A year later, Michael transferred
to Heidelberg for two years of study under the renowned
Bunsen, who ever remained his scientific paragon. He returned
to Berlin in 1876 for two years of study, and it was then that
he began the execution and publication of his remarkably long
series of brilliant and important researches. Hofmann was the
outstanding organic chemist of Germany and his laboratory at
that time was the focal point of the world for research in organic
chemistry, and there Michael became acquainted with many
of the future leaders in that field, among them Ira Remsen
and our own Charles Loring Jackson. Michael concluded his
student years by spending another year at the Ecole de Me'decine
in Paris under the great Wurtz.
"In 1880, Michael returned to America, and after a short
period as Assistant in the Chemical Laboratory at Tufts Col-
lege, was appointed Professor of Chemistry at that institution.
He was able to devote practically all of his time to research and
with the aid of private assistants and graduate students prose-
cuted his investigations with great energy and success. Among
the graduate students who came to study with him at that time
was Miss Helen Abbott of Philadelphia. She and Michael were
married in 1889, and after an 18 months' tour around the world,
Michael accepted a position as Head of the Department of
Chemistry at the recently established Clark University. This
position soon proved most uncongenial, and after a few months
he resigned and established a residence and a private laboratory
on the Isle of Wight, where he pursued his researches for four
years. In 1894, he resumed his professorship at Tufts College
and remained there until 1907 when he became Professor
Emeritus, whereupon he established a private laboratory on his
estate at Newton Center.
"In 1912, Michael was appointed Professor of Organic
Chemistry at Harvard. He gave no lecture courses. At first his
OCR for page 333
ARTHUR MICHAEL
333
research students and his private assistants worked with him in
his laboratory at Newton Center, but during his later years,
they carried on their experimental work at the Converse Lab-
oratory, reporting at frequent intervals to Professor Michael at
his home. Michael became Emeritus here in 1936, nineteen
years after he had taken a similar status at Tufts College.
"Next to chemistry, Michael's chief interest was in art,
especially ancient and medieval art. He began collecting at an
early date and his home in Newton was a repository of thou-
sands of rare objects of art. Through his friendship with Pro-
fessor Fenollosa, his attention had been directed particularly
to oriental art, and objects from the Orient were numerous
and conspicuous in his collections. He also had a fine collec-
tion of Early American silver. As might have been expected,
Michael's erudition regarding the innumerable items of his
collection was encyclopedic. At his death he bequeathed his
American silver to the Smithsonian Institution and the
mainder of his collection to the Albright Art Gallery in his
native city of Buffalo.
"As a young man, Michael passed many of his vacations
among the mountains; the Alps, the Canadian Rockies, and the
Selkirks. Indeed, he became a real mountain climber. Thus,
in 1897, he was in the party that made the first ascent of Mount
Lefroy, and a few days later, with Professor Fay of Tufts College,
he made the first ascent of Mt. Victoria. These are the two
splendid ice-capped peaks which dominate the vista at Lake
Louise.
re-
.
"Michael was an eager, alert, but retiring personality, deeply
Immersed in his scientific and artistic pursuits. He had few
intimates and he shunned publicity. Indeed, he declined to
accept the award of a famous medal because of the publicity
which this would entail. As a teacher, he was stimulating and
inspiring and uncompromising in his insistence on thorough-
ness and accuracy. In his home, among his beautiful Chinese
porcelains and bronzes, his Greek and Roman statuettes, his
OCR for page 334
334
BIOGRAPHICAL MEMOIRS
medieval works of art, with his extraordinary cosmopolitan
background of experience and acquaintance, he was an incom-
parable host.
"Michael was always very fond of children, although he
never had any of his own. It is not surprising, therefore, that
in his will, after disposing of his art collection, his library, and
his chemical apparatus, he bequeathed the residue of his
considerable estate to three Buffalo institutions for the care
of crippled, blind and needy children.
"Michael's research activities were prodigious and remark-
ably prolonged. The first of his 225 separate articles describing
his researches was published when he was twenty-three years
old; the last appeared a few months after his death sixty-six
years later. It would be idle to attempt to recapitulate these
many contributions; a few may be mentioned for which he
will be particularly remembered.
"Michael was the first to synthesize a natural glucoside
(helicin, 1879), and the method that he introduced has become
the standard synthetic route to this important class of com-
pounds. Another landmark was his discovery, in 1887, of the
addition of active-hydrogen reagents to a!,,B-unsaturated esters
and carbonyl compounds; this, the Michael reaction, proved
capable of wide elaboration and, in one or another of many
modifications, constitutes an important tool of the modern
builder of molecules. Another general synthetic method dis-
covered by Michael, a modification of the Perkin Reaction, is
extensively used for the condensation of aldehydes and malonic
acid (1883~. Finally may be mentioned his discovery of chlorine
heptoxide, in 1900.
"This enumeration might seem to imply that Michael was
concerned chiefly with the experimental rather than the theo-
retical aspects of chemistry. Actually the very opposite was the
case. Michael was passionately interested in the theories of
organic chemistry; that is, the fundamental laws and the
mechanisms which might explain the marvelous variety and
OCR for page 335
ARTHUR MICHAEL
335
multiplicity of the compounds of carbon. All of his researches
were undertaken to shed some light on these fundamental ques-
tions, and his numerous and far-ranging experimental investi-
gations did, as a matter of fact, lead to the elaboration of a
general theory of organic reactions. He developed special con-
ceptions of the nature of valence, the condition of unsaturated
systems, and the forces involved in chemical reactions, and he
formulated a principle according to which 'every chemical
system tends to so arrange itself that the maximum of chemical
neutralization is attained.'
"While a few of Michael's collaborators learned to apply
his method of reasoning, the Michaelian theories have had but
little following, even though accorded the prominence of a
special chapter in F. Henrich's treatise on the Theories of
Organic Chemistry. Nevertheless, Michael himself, with his
keen intuitive faculty, his wide experience in the laboratory,
and his vast knowledge of the literature, could apply these
concepts with extraordinary success both in the interpretation
of known phenomena and in the prediction of unexplored
happenings. Theories that can be thus applied certainly have
a prima facie justification.
"The vigor of Michael's interest in theory and his extreme
independence of thought were responsible for another im-
portant function which he performed throughout his long
career to the great advantage of chemical science, namely, that
of a sharp and penetrating critic of accepted views.
"When the van's Hoff theory of geometrical isomerism was
gaining general acceptance through the able exploitation of
Wislicenus and others, Michael flatly refused to accept what
to him was an unproved hypothesis. Alert to any opportunity
to attack current doctrine, he saw the weakness in Wislicenus'
assumption that additions to unsaturated substances necessarily
proceed in the cis direction and, in- a series of carefully planned
experiments, proved conclusively that bans addition does in-
deed occur. He thereby corrected an erroneous feature of this
OCR for page 336
336
BIOGRAPHICAL MEMOIRS
theory, but far from overthrowing the basic theory itself, his
work extended and greatly strengthened a general concept that
soon became a fully established tenet of the science. This ex-
ample can be amplified by many others. Victor Meyer's view
that the sulfone grouping is not comparable with the carbonyl
and other acid-formina radicals was generally accepted until
Michael (1889) succeeded in demonstrating the reactivity of the
methylene groups in,8-sulfonyl esters. Michael was the first to
question the C-metal formulation of the metal derivatives of
nitroparaffins (1888), and, in 1908, he challenged Claisen's views
with regard to the relative stabilities of enolates. In 1920 he
severely criticized Tiffeneau's interpretation of the pinacol and
benzilic acid rearrangements, and, in 1935, he attacked the
experimental basis for analogies accepted over a period of years
v , ~
as supporting the hypothetical addition—elimination mechan-
ism of aromatic substitutions. His own astutely planned and
faultlessly executed reinvestigations of the nitration and sul-
fonation of olefins proved the previously accepted analogies to
be nonexistent, and indeed the hypothesis that he contested is
now discarded.
"Summarizing, we can say that Michael was a powerful
theorist, a keen critic and a consummate experimentalist. Or
perhaps with equal appropriateness we can in conclusion quote
the citation opposite his name in American Men of Science
describing his field of activity, which reads, "Investigations in
organic chemistry bearing on its fundamental laws and theory."
In a review of the Michael reaction published 112 years
after the initial discovery, E. D. Bergmann, D. Ginsburg, and
R. Pappy cite 1045 references to its exploration and use. They
note that in its original scope the condensation is a base-catalyzed
addition of an addend or donor (A) containing an c'-hydrogen
atom in the system O C—CH to a carbon-carbon double bond
that forms part of a conjugated system of the general formula-
~ E. D. Bergmann, D. Ginsburg, and R. Pappo, "The Michael Reaction,"
Organic Reactions 10(1959):179.
OCR for page 337
ARTHUR MICHAEL
337
tion C C—C O in an acceptor (B). Typical acceptors are
cY,,8-unsaturated aldehydes, ketones, and acid derivatives. All
R Ri R3 Rs R6
I ~ ~ ~ ~ Base
O=C—CH + C: C—C- O
1 2 1 4
A
B
R R1 R3 R5 R6
1 1 1 1 1
O C—C—C—C—CO
1 2 1 4 1
structures containing 0 C—CH— in which the hydrogen is
active by the Zerewitinoff test will serve as donors in the Michael
reaction. In addition, many compounds that do not meet this
test of hydrogen activity, such as acetophenone, are effective
Michael reactants. Typical acceptors are ~,,8-unsaturated alde-
hydes, ketones, and acid derivatives. By extension of the orig-
inal scope, the Michael reaction has come to be understood to
include addends and acceptors activated by groups other than
carbonyl and carboalkoxyl. The wider scope includes as donors
nitrites, nitro compounds, sulfones, and certain hydrocarbons
such as cyclopentadiene, indene, and fluorene that contain suf-
ficiently reactive hydrogen atoms. Another hydrocarbon ac-
ceptor is the conjugated tetraacetylenic compound (I), which
adds diethyl sodium malonate as follows:
CH3C_C—C_C—C_C—C_CCH3 + CH2(C02C2H~2
(I)
Base
CH3C_C—C_C—C—C—CH C(CH3)CH(CO2C2H5)~
The review article cited discusses the mechanism of the
Michael reaction, the nature of the anion of the adduct, and
the reverse, or retrograde Michael reaction, used for example in
establishing the course of the biosynthesis of cholesterol, the
question of para-bridged intermediates, the stereochemistry of
the Michael condensation, and related topics. In presentin~ a
OCR for page 338
338
BIOGRAPHICAL MEMOIRS
brief sketch of "an almost legendary figure, one of those giants
of the days of the dawn of organic chemistry," W. T. Read ~
described Michael as "one of the most interesting figures that
has ever appeared in the scientific world." In another review t
Professor Albert B. Costa, historian of science of Duquesne
University with research interests in nineteenth-century organic
chemistry, described Michael's synthesis of natural glucosides
and noted his preparation of pyrimidines by the reaction of
ureas or thioureas with ethyl sodiomalonate. However, he
states:
"Michael's primary concern was not these experimental con-
tributions but organic theory. So concerned was he with funda-
mental principles that he elaborated a general interpretation of
organic reactions and developed his own conceptions of the
forces involved in chemical phenomena.! Energy conversions
were for him the important controlling factors in all chemical
changes, and he interpreted organic reactions in terms of energy
in a long series of papers from 1888 on. His novel contribution
to chemical theory was to introduce the thermodynamic con-
ceptions of free energy and entropy into organic structural
theory in order to overcome the pictorial and mechanical inter-
pretation of chemical behavior.
"Michael's speculations included the genesis of the chemical
elements in energetic terms (1910~. The original corpuscles of
matter were exclusively carriers of free chemical energy (con-
vertible into less active chemical and physical energy), and
all of the bound chemical energy (only partially reconvertible
into free energy) appeared gradually in time from this original
reservoir of free energy. Adopting the chemical evolutionary
~ W. T. Read, "American Contemporaries; Arthur Michael," Industrial and
Engineering Chemistry 22(1930):1137.
t A. B. Costa, "Arthur Michael (1853-1942). Meeting of Thermodynamics and
Organic Chemistry," Journal of Chemical Education 48(1971):243.
:t F. Henrich, Theories of Organic Chemistry, transl. T. B. Johnson and D. A.
Hahn (New York: John Wiley & Sons, Inc., 1922).
OCR for page 339
ARTHUR MICHAEL
339
ideas then in vogue, he argued that the elements appeared in
sequential order. In the earlier stages of the formation of the
atoms of the elements the free energy of the original corpuscles
was converted largely into bound energy and heat; thus, the
atoms of the less active elements were formed. As the tempera-
ture rose in the process of chemical evolution, such extensive
conversions of free into bound energy did not occur and more
reactive elements gradually emerged. With the genesis of the
radioactive elements there appeared atoms with so much free
energy that they were unstable.
"Having the chemical elements with their varying degrees
of activity based on their free energy content, Michael set out
to interpret chemical reactions. His starting point was Kekule's
idea that the first stage in every chemical reaction consisted in
two molecules attracting each other through their chemical
affinity to form a double molecule. Michael proposed that the
free chemical energy in two unlike molecules was converted in
part into bound energy and heat, the stability of the double
molecule being determined by the extent of this conversion.
He represented the reaction between sodium and chlorine in
the following manner, using dotted lines to represent the free
energy and solid lines the bound energy of atoms.
' ' ' Na Na
1
Na—Na + C1 C1 ~
C1 -C1
1
1
Na Na
1 1
C1 C1
Na Na
1 1
C1 C1
Na Na
1 1 1
2NaC1
(1)
(2)
(3)
OCR for page 340
340
BIOGRAPHICAL MEMOIRS
"In phase (1) the free energy in sodium and chlorine mole-
cules resulted in the formation of a double molecule of the
elements. Phase (2) represented the neutralization of the free
-energy as completely as possible. Finally, the bound energy
between the two sodium atoms and two chlorine atoms was
converted into bound energy between sodium and chlorine, the
energy of the like atoms not being sufficient to hold these atoms
together.
"In general, every spontaneous chemical change involved
the conversion of free into bound energy. Every atom repre-
sented a Reunite quantity of potential chemical energy and
had a tendency toward a condition of greater stability. Free
energy and the affinity relationships of the atoms determined
the chemical potential of a system.
"To Michael, the second law of thermodynamics was the most
firmly established generalization in science. The increase in
entropy that took place in every spontaneous chemical change
must be the soundest-basis for organic theory. For entropy, he
substituted 'chemical neutralization,' meaning by this the neu-
tralization of the free energy of the reacting atoms. The greater
the conversion of free into bound energy that took place the
more the neutralization of the chemical forces of the atoms. He
then restated the second law in chemical terms: 'Every chemical
system tends to arrange itself so that the maximum of chemical
neutralization is attained.'
"Michael applied this general theory in detail to organic
chemistry. Molecular rearrangements, addition and substitution
reactions, tautomerism, and stereochemical phenomena were
among the aspects of organic chemistry included within his
theory. In the case of molecular rearrangements he proposed
four factors which determined whether rearrangements might
occur: (1) the extent of free energy among the interchanging
atoms or groups; (2) their affinity for each other and for the
atoms in the group to which they migrate; (3) the amount of
. ~ ~ .
OCR for page 357
ARTHUR MICHAEL
357
Vierter abschnitt: uber die gesetze der Alloisomerie und Anwen-
dung derselben zur Classificirung ungesattigter organischer Ver-
bindungen. l. prakt. Chem., 52:344.
Bemerkungen zu Arbeiten von C. A. Bischoff, ~. A. Wislicenus and
t. H. van's Hoff.
J. prakt. Chem., 52:365.
1896
Uber die Einwirkung von Athyljodid und Zinc auf ~-Fettester.
Ber. dtsch. chem. Ges., 29:1791.
With l. E. Bucher. Zur Constitution der Oxalessigsaure. Ber.
dtsch. chem. Ges., 29:1792.
Zur Kenntniss der Additionsvorgange bei den Natriumderivaten
von Formyl- und Acetessigestern und Nitroathanen. Ber. dtsch.
chem. Ges., 29:1793.
Herrn. E. Erlenmeyer und C. Liebermann zur Erwiderung. l.
prakt. Chem., 54:107.
1898
With l. E. Bucher. On the action of acetic anhydride on phenyl-
propiolic acid. Am. Chem. J., 20:89.
With F. Luehn and H. H. Higbee. On the formation of imido-
1,2-diazol derivative from aromatic azimides and esters of ace-
tylenecarboxylic acids. Am. Chem. i., 20:377.
Uber das Verhalten von Benzaldehyd gegen Phenol. l. prakt.
Chem., 57:334.
1899
Uber die Ersetzung des Natriums in Natriumphenylsulfonessigester
durch Alkyle. J. prakt. Chem., 60:96.
Uber einige Gesetze und deren Anwendung in der organischen
Chemie. I. [. prakt. Chem., 60:286.
With V. L. Leighton.
Uber einige Gesetze und deren Anwendung
in der organischen Chemie. II. J. prakt. Chem., 60:409.
With W. T. Conn. On chlorine heptoxide. Am. Chem. i., 23:444.
1900
Zur Kenntniss der Natriumacetessigestersynthese und der Vierring-
bildung mittels Natriumathylats. Ber. dtsch. chem. Ges., 33:
3731.
OCR for page 358
358
BIOGRAPHICAL MEMOIRS
1901
With W. T. Conn. On the behavior of iodine and bromine toward
chlorine heptoxide and perchloric acid. Am. Chem. T.. 25:89.
Zur Kenntniss der Perkin'schen Reaction.
34:918.
~ ,
Ber. dtsch. chem. Ges.,
On methyl cyanide as a catalytic reagent and a criticism of i. U.
Nef's views on the Frankland-Wurtz- and Conrad reactions.
Am. Chem. T., 25:419.
With V. L. Leighton and F. D. Wilson. Uber die isomeren Iso-
butylenchlorhydrine und die Zersetzung der gemischten Aether
durch Halogenwasserstoff. .T- prakt. Chem., 64:102.
Zur Kenntniss der drei stereomeren Zimmtsauren. Ber. dtsch.
chem. Ges., 34:3640.
With W. W. Gerner and W. H. Graves. Zur Kenntniss der Sub-
stitution-vorgange in der Fettreihe. Ber. dtsch. chem. Ges.,
34:4028.
·e
Uber einige Laboratoriumsapparate. Ber. dtsch. chem. Ges., 34:
4058.
With T. H. Mighill. Zur Kenntniss des Additions-Abspaltungs-
Gesetzes. Ber. dtsch. chem. Ges., 34:4215.
1903
Bemerkung zur der Mittheilung des Hrn. S. Svoboda "Uber einen
abnormalen Verlauf der Michael'schen Condensation." Ber.
dtsch. chem. Ges., 36:763.
With W. W. Garner. Beitrage zur Frage der Isozmutsaure. Ber.
dtsch. chem. Ges., 36:900.
Zur Geschichte der Isozimmtsaure. Ber. dtsch. chem. Ges., 36:2497.
On the condensation of oxalic ethylester with ethylene and tri-
methylene cyanides. Am. Chem. i., 30:156.
Valenzhypothesen und der Verlauf chemischer Vorgange. i. prakt.
Chem., 68:487.
With V. L. Leighton. Uber die Konstitution des Phenylcinna-
menylakrylsauredibromids. J. prakt. Chem., 68:521.
1905
Phenylisocyanat als Reagens zur Feststellung der constitution tauto-
merer Verbindungen. Ber. dtsch. chem. Ges., 38:22.
OCR for page 359
ARTHUR MICHAEL
~q
·.
With O. Eckstein. Uber die Bildung von o-Acylderivaten aus
Cyanessigester durch Anwendun~ von Pvridin und Chinolin.
Ber. dtsch. chem. Ges., 38:50.
O ,
Zur Geschichte der Theorie uber die Bildung und Constitution
des Natracetessigesters. Ber. dtsch. chem. Ges., 38:1922.
Zur Kenntniss der Synthesen mit Natracetessigester. Ber. dtsch.
chem. Ges., 38:2096.
Zur Frage uber der Verlaug der Claisen'schen Zimmtsaurestersyn-
these. Ber. dtsch. chem. Ges., 38:2523.
Zur Kenntniss der Vorgange bei der Synthesen mit Natrium
Malonester und verwandten Verbindungen. Ber. dtsch. chem.
Ges., 38:3217.
Herren Stormer und Kippe zur Erwiderung.
Ges., 38:4137.
Ber. dtsch. chem.
Uber die Darstellung reiner Alkylmalonester. t. prakt. Chem.,
72:537.
1906
On the isomerism and tautomerism question.
201.
Am. Chem. J., 35:
With H. D. Smith and A. Murphy, in The question of isomerism
and tautomerism. Ber-. dtsch. chem. Ges., 39:203.
Zur constitution des Tribenzoylenbenzols. Ber. dtsch. chem. Ges.,
39:1908.
With W. W. Garner. Cinnamylideneacetic acid and some of its
transformation products. Am. Chem. l., 35:258.
With W. W. Garner. Magnesium permanganate as an oxidizing
agent. Am. Chem. l., 35:267.
Zur constitution des "Kohlensuboxyds." Ber. dtsch. chem. Ges.,
39:1915.
Uber das Vertheilungsprincip. Ber. dtsch. chem. Ges., 39:2138.
Uber den Verlauf der addition von Wasser an Hexin-2. Ber. dtsch.
chem. Ges., 39:2143.
With R. N. Hartman. Zur Constitution des aus Mannit-Hexen
dargestellten Hexylalkohols. Ber. dtsch. chem. Ges., 39:2149.
Uber die Einwirkung von Chlor auf Hexan. Ber. dtsch. chem.
Ges., 39:2153.
With V. L. Leighton. Uber die Addition von Unterchloriger saure
an Isobuten. Ber. dtsch. chem. Ges., 39:2157.
With F. D. Wilson. Uber den Verlauf der Zersetzung von gemi-
OCR for page 360
360
BIOGRAPHICAL MEMOIRS
schten Fettathern durch ~odwasserstoffsaure. Ber. dtsch. chem.
Ges., 39:2569.
Uber die Einwirkung von Salzsaure auf Propenoxyd und Propen-
alkohol. Ber. dtsch. chem. Ges., 39:2785.
Uber die Einwirkung von Salzsaure auf
With V. L. Leighton.
Isobutenoxyd. Ber. dtsch. chem. Ges., 39:2789.
With A. B. Lamb. The isomerism of ethyl coumaric and ethyl
coumarinic acids. Am. Chem. l., 36:~52.
1907
With R. N. Hartman. Zur Konstitution des aus Mannit darge-
stellten Hexyljodids. Ber. dtsch. chem. Ges., 40: 140.
With H. Hibbert. On the ammonia reaction as a means of dis-
tinguishing between enol and keto derivatives. I. Ber. dtsch.
chem. Ges., 40:4380.
With H. Hibbert. The ammonia reaction as a means of distin-
guishing between enol and keto derivatives. II. Ber. dtsch.
chem. Ges., 40:4916.
Die van's Hoff-Wislicenusache
Chem., 75: 105.
Konfigurationslehre. .T. prakt.
1908
Stereoisomerism and the law of entropy. Am. Chem. .~., 39:1.
VVith H. D. Smith. The addition of halogens to cinnamic acid and
some of its derivatives. Am. Chem. J., 39:16.
Uber Desmotropie und Merotropie. I. Ann. Chem., 363:20.
With H. D. Smith. II. Die tertiaren Amine als Reagentien zur
Unterscheidung zwischen stabilen Enol- und Ketonderivaten.
Ann. Chem., 363:36.
With P. H. Cobb. III.
der Constitution Merotropen Vergindungen. Ann. Chem.,
363:64.
With A. Murphy, Jr. IV. Acetylchlorid und Essigsaureanhydrid
als Reagentien zur Unterscheidung zwischen Enol- und Keton-
derivaten. Ann. Chem., 363:94.
Phenylisocyanat als Reagens zur Festellung
With W. W. Garner. Magnesium permanganate as an oxidizing
agent. Monatshefte fuer Chemie und Verwandte Teile Anderer
Wissenschaften, 22:556.
With.J. E. Bucher. Zur Frage uber die Festellung der Konstitution
OCR for page 361
ARTHUR MICHAEL
361
der Phenylnaphthalindicarbonsaure; Hrn. Hans Stobbe zur
Antwort. Ber. dtsch. chem. Ges., 41:70.
·.
Uber refraktometrischen Beweis der Konstitution des "Kohlen-
suboxyds." Ber. dtsch. chem. Ges., 41:925.
With H. Hibbert. Uber die vermeintliche Beziehung zwischen
Dielektrizitatskonstante und isomerisierender Kraft organischer
Losungsmittel bei Enol-Keton-Desmotropen. Ber. dtsch. chem.
Ges., 41:1080.
·—
With O. D. E. Bunge. Uber den stereochemischen verlauf der
Addition von Chlor zu Crotonsaure. Ber. dtsch. chem. Ges.,
41:2907.
1909
With H. Hibbert. V. Zur Constitution des Cyanwasserstoffs. Ann.
Chem., 364:64.
With H. Hibbert. VI. Zur Constitution der Cyansaure. Ann.
Chem., 364:129.
With R. F. Brunel. On the relative ease of addition in the alkene
group. First paper on the laws of addition in organic chemistry.
Am.Chem. [.,41:118.
Zur theorie der Esterfikation organischer Carbonsauren. (Erste
Mitteilung uber die Natur der "sterischen Hinderung"~. Ber.
dtsch. chem. Ges., 42:310.
·—
With K. ~. Oechslin. Uber den Einfluss der substituenten aro-
matischer Carbonsauren auf ihre Esterifikation. II. Ber. dtsch.
chem. Ges., 42:317.
Das chinon von Standpukt des Entropiegesetzes und der Partialva-
lenzhypothese. T. prakt. Chem., 79:418.
·.
With K. Wolgast. Uber die Beziehung zwischen Struktur des Fet-
talkohole und Geschwindigkeit der Esterifikation. III. Ber.
dtsch. chem. Ges., 42:3157.
With K. ~rolgast. Zur Darstellung reiner Ketone mittels Acetes-
sigester. Ber. dtsch. chem. Ges., 42:3176.
1910
.—
Uber die Beziehung zwischen Structure der Fettalkohole- und
geschwindigkeit der Esterifikation. Ber. dtsch. chem. Ges.,
43:464.
..
Uber die "Additionstheorie," Hrn. S. l. Acree zur antwort. Ber.
dtsch. chem. Ges., 43:621.
OCR for page 362
362
BIOGRAPHICAL MEMOIRS
On the application of physical chemical methods to determine the
mechanism of organic reactions. Am. Chem. I., 43:322.
Outline of a theory of organic chemistry founded on the law of
entropy. J. Am. Chem. Soc., 32:990.
With A. Murphy, in On the action of chlorine in solution in car-
bon tetrachloride and of carbon tetrachloride on metallic oxides.
Am. Chem. I., 44:365.
With P. H. Cobb. Uber die Reaktion zwischen Chinon und Salz-
saure. I. prakt. Chem., 82:297.
Uber den Mechanismus der Chinonreaktionen. Hrn. Theodor
Posner zur erwiderung. I. prakt. Chem., 82:306.
1911
With H. Leupold. Zum verlauf der intramolekularen Umlagerun-
gen bei den Alkylbromiden und zur Frage der Ursacl~e des
Gieichgewichtszustandes bei Unkehrbaren reaktionen. Ann.
Chem., 379:263.
1912
With R. F. Brunel. Action of aqueous solutions of acids on alkenes.
Am. Chem. i., 48: 267.
With F. Zeidler. Chemistry of the amyl series. Ann. Chem., 385:
227.
Number of isomers in merotropic and desmotropic compounds. I.
Ann. Chem., 390:30.
Number of isomers in merotropic and desmotropic compounds. II.
Isomeric keto forms of acetyldibenzoylmethane. Ann. Chem.,
390:46.
\Vith Harold Hibbert. Number of islanders in merotropic and des-
motropic compounds. III. Isomeric keto forms of propionyl-
dibenzoylmethane. Ann. Chem., 390:68.
Number of isomers in merotropic and desmotropic compounds. IV.
Isomeric forms of formylphenylacetic ester. Ann. Chem., 391:
235.
With G. P. Fuller. Number of isomers in merotropic and des-
motropic compounds. Isomeric enol forms of formylphenylacetic
ester. Ann. Chem., 391:275.
With F. Zeidler. Course of intramolecular rearrangements in alkyl
bromides. Ann. Chem., 393:81.
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ARTHUR MICHAEL
363
Application of the "scale of combined influence" to explain the ioni-
zation constants of organic acids, and a reply to C. G. Derik.
i. Am. Chem. Soc., 34:849.
1913
The Perkin reaction. Am. Chem. i, 50:4 1 1 .
·—
With E. Scharf. Uber den Mechanisms der Einwirkung van Brom
auf Fettsaurechloride. Ber. dtsch. chem. Ges., 46:135.
1914
With W. Schlenk, l. Appenrodt and A. Thal. Uber Metalladi-
tionen en mehrfache Bindungen. Ber. dtsch. chem. Ges., 47:473.
Number of isomers of merotropic and desmotropic compounds. VI.
Isomeric forms of formylphenylacetic ester. Ann. Chem.,
406:137.
1916
With E. Scharf and K. Voigt. Rearrangement of iso into tertiary
butyl bromide. l. Am. Chem. Soc., 38:653.
1918
Configurations of organic compounds and their relation to chemical
and physical properties. I. Am. Chem. Soc., 40:704.
Configurations of organic compounds and their relation to chemical
and physical properties. II. The relations between the physical
properties and the configurations of unsaturated acids. J. Am.
Chem. Soc., 40: 1674.
1919
Relations between the chemical structures of carbonyl derivatives
and their reactivities towards salts of semicarbazide. J. Am.
Chem. Soc., 41:393.
1920
The chemical mechanism of organic rearrangements.
Soc., 42:787.
J. Am. Chem.
The non-existence of valence and electronic isomerism in hydroxyl-
ammonium derivatives. i. Am. Chem. Soc., 42:1232.
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364
BIOGRAPHICAL MEMOIRS
1921
The structures and reactions of hydroxylamine and its derivatives.
I. i. Am. Chem. Soc., 43:315.
1929
Castor-oil preparation.
Australian patent 20,127.
1930
With l. Ross. Course of addition of sodium enol alkyl malonic
esters to c~,,8-unsaturated esters. I. Am. Chem. Soc., 52:4598.
1931
With I. Ross. Course of addition of sodium enol alkylmalonic and
sodium enol alkylcyanoacetic esters to unsaturated esters. I. Am.
Chem. Soc., 53:1150.
With i. Ross. c~,3^y-Trimethylglutaric acids. l. Am. Chem. Soc.,
53:1175.
With J. Ross. Partition principles as applied to the structures of
enolic sodium derivatives of 1,3-diketones and ,8-keto esters.
[.Am. Chem. Soc., 53:2394.
1932
With l. Ross. Partition principles as applied to the structure of
enolic sodium derivatives of 1,3-diketones and ,B-keto esters. II.
J.Am.Chem.Soc., 54:387.
With i. Ross. Addition of sodium enol alkylmalonic ester to benzal-
acetophenone. T. Am. Chem. Soc., 54:407.
1933
With I. Ross. Course of addition of the sodium enolates of malonic
and methylmalonic esters to benzalacetophenone and to crotonic
ester. I. Am. Chem. Soc., b5: 1632.
With l. Ross. Carbon syntheses with malonic and related acids.
1. i. Am. Chem. Soc., b5: 3684.
1934
With N. Weiner. Formation of enolates from a-lactonic esters. l.
Am. Chem. Soc., 56:2012.
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ARTHUR MICHAEL
1935
365
With G. H. Carlson. Mechanism of reactions of acetoacetic ester,
the enolates and structurally related compounds. I. C- and O-
Alkylation. i. Am. Chem. Soc., 57:159.
The mechanism of the reactions of metal enol acetoacetic ester and
related compounds. II. Sodium enolates toward acyl chloride.
I. Am. Chem. Soc., 57:165.
With G. H. Carlson. Mechanism of the nitration process. l. Am.
Chem. Soc., 57:1268.
1936
\Vith N. Weiner. Mechanism of the sulfonation process. T. Am.
Chem. Soc., 58:294.
I\Iechanism of the reactions of metal enol acetoacetate ester and
related compounds. III. Copper enolates. T. Am. Chem. Soc.,
58:353.
\\lith N. Weiner. Carbon syntheses with malonic acid and related
compounds. II. Aromatic aldehydes.~ I. Am. Chem. Soc., 58:680.
With N. Weiner. Formation of enolates from lactonic esters. l.
Am. Chem. Soc., 58:999.
1937
With N. Weiner. 1,2- and 1,4-Addition. I. The 1,4-addition of
potassium isocyanate. I. Am. Chem. Soc., 69:744.
With G. H. Carlson. 1,2- and 1,4-Addition. II. Nitrogen tetroxide
and trimethylethylene. l. Am. Chem. Soc., 59:843.
Course of the addition of malonic enolates to a,,8-unsaturated esters.
J. Org. Chem., 2:303.
1938
\Vith N. Weiner. The partition principle as applied to the struc-
tures of enolic sodium derivatives of ,8-diketones and ,8-keto
esters. III. l. Org. Chem., 3:372.
1939
With G. H. Shadinger. Influence of solvents on the stereochemical
course of the addition of hydrogen bromide to monobasic acety-
lenic acids and the relation of solvent effect to chemical structure.
I. Org. Chem., 4:128.
OCR for page 366
366
BIOGRAPHICAL MEMOIRS
With G. H. Carlson. 1,2- and 1,4-Addition. III. Nitrogen trioxide
and trimethylethylene. I. Org. Chem., 4:169.
The relations of "oxygen and peroxide effect," and of hypochlorous
acid addition, to the structures of unsaturated organic com-
pounds. I. Org. Chem., 4:519.
With N. Weiner. Solvent and peroxide effect in the addition of
hydrogen bromide to trimethylethylene. I. Org. Chem., 4:531.
1940
With G. H. Carlson. 1,2- and 1,4-Addition. IV. Nitrogen tetroxide
and isobutylene. I. Org. Chem., 5: 1.
\Vith G. H. Carlson. 1,2- and 1,4-Addition. V. Nitrogen tetroxide
and tetramethylethylene. l. Org. Chem., 5:14.
With N. Weiner. Solvent and peroxide effect in the addition of
hydrogen bromide to unsaturated compounds. IV. Isopropyl-
ethylene. I. Org. Chem., 5:389.
1943
With C. M. Saffer, fir. The addition of triphenylmethylsodium and
phenyllithium to cinnamic ester and benzalacetophenone. J.
Org. Chem., 8:60.
With H. S. Reason. Normal addition of hydrogen bromide to 3-
butenoic, 4-pentenoic and 5-hexenoic acids in hexane. I. Am.
Chem. Soc., 65:683.
With H. S. Mason. Determination of the composition of mixtures
of c'-bromo-c'-methyl, and cY-bromo-,8-methylsuccinic acids. l.
Org. Chem., 9:393.
OCR for page 367
Representative terms from entire chapter:
arthur michael
