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Otto Roelen Pioneer in Industrial Homogeneous Catalysis.

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Otto Roelen, Pioneer in Industrial Homogeneous Catalysis
Boy Cornils,* Wolfgang A. Herrmann, and Manfred Rasch
Otto Roelen discovered the 0x0 synthesis (hydroformylation) in 1938, and
despite all the problems created by the
war ycars he was able to explore successfully the fundamental aspects related to
its application up to the point of building
the first plant. At the same time he laid
the groundwork for industrial utilization of homogeneous organometallic
catalysts. Almost simultaneously. his
contemporary, Walter Hieber, was investigating the basic chemistry of the same
catalysts. but with no knowledge whatsoever of their potential application. Hydroformylation today constitutes one of
the most important industrial examples
of a homogeneous catalytic process.
A unique opportunity for academic
and industrial chemists to engage in a
goal-oriented collaborative effort with
respect to an important new synthetic
method was missed in this case, however-missed less as a consequence of
events of the day than because of the dif-
fering mentalities of two difficult personalities. In less turbulent times these two
unpredictable individuals might well
have collaborated. A number of contemporary documents published here
for the first time, supplemented by
Allied reports related to “hidden reparations,” provide interesting insights into
the nature of this particular discovery
and its subsequent course of development.
1. The Researcher and the Man:
University, Research Institute, and Industry
. .that Herr dipl. Ing. Roelen has been educated both theoretically and practically to such an extent that he would represent no obstacle to further progress in the work being conducted there. To all intents and purposes, R. carried out his
thesis work completely independently, indeed very reliably,
and with an equivalent amount ofdiligence. The only thing I
might criticize is his tendency to theorize, but this is probably
onl!. ;I result of the fact that R . did an unbelievable amount
of both work and reading. With respect to his knowledge, R.
is far above the average for other doctoral candidates.”[**’
This brief report accurately describing the distinguishing
characteristics of its subject was written by Prof. Alexander
Gutbier of the Laboratory for Inorganic Chemistry and Inorganic Chemical Technology at the Technische Hochschule Stutt[*IProl. Dv. B. C‘ornils
Hoeclist AG. D-65926 Fi-ankfurt a m Main
T c l c l a \ ’ 1111 code
Pi-of Lk. W. ‘4. Herrinanii
. 4 n n i - g a n i ~ c h - c l i e r n i s ~lnstitut
dci Tcchnlichen Univsrsirit Munchen
Lichknbergstr.isse 4. D-85747 (;arching (FRG)
L k hl Ra\ch
Thv\\cii .A(;. Archiv
D J 7 l h l D u i h i r g (FRG)
Thc oiiginal Gerinan quotations may he found i n the Gcrman issuc,
C‘/i<Jliii<z 1994. 106. 2219-2238
gart and accompanied Otto Roelen on June 26, 1922 when he
arrived at the Kaiser-Wilhelm-Institut fur Kohlenforschung
(KWI) in Mulheim an der Ruhr. where he would begin work
under the supervision of Prof. Franz Fischer, Director of the
Institute, and Fischer’s Section Leader, Dr. Hans Tropsch. in
the general area of hydrocarbon synthesis.“]
Although Otto Roelen was himself born in Mulheim on March
22, 1897, and as a high school student witnessed the official dedication of the KWI on July 27, 1914, his future career was in no
sense as predestined as it might appear in retrospect. Roelen attended the Konigliche Realgymnasium (Royal High School) in
his hometown. where he was awarded a wartime diploma on
August 4, 1914. He did not immediately volunteer for military
service, however, choosing instead to serve a six-month internship at the nearby blast furnace m d foundry works of the
Friedrich Wilhelms-Hutte before registering as a chemistry student at the Technische Hochschule Miinchen. He was one of
only 21 students there between 1914 and 1918, and must have
taken the introductory chemistry course taught by Wilhelm
Manchot (cf. Section 3.1). Roelen was finally drafted in July of
1915, and participated as an artillerist in the battles in Flanders,
where he was wounded in 1917. At that time he held the rank of
artillery mate with the 2nd Marine Artillery Division of the 2nd
Heavy Corps Artillery Regiment.[*]Subsequent to his injury he
was no longer considered fit for active duty, and was employed
as a “chemical technician” at the Royal Submarine Shipyard in
Wilhelmshaven, where he was stationed when the war ended. By
his own report he had joined a local Workers’ and Soldiers’
Otto Roelen
Council (“Arbeiter- und S~ldatenrat”).[~]
but nothing is known
regarding the reasons for his apparent participation in the
Council Movement, and there is in fact no independent documentation of this involvement. Indeed, it seems quite inconsistent with his later attitudes, and he was never again active in
politics. His alleged membership in the Wilhelmshaven Workers‘ and Soldiers’ Council may simply have served as a protective shield during the British “denazification” process. in which
Roelen wiis classified as presenting “no objection,” and he never
mentioned the matter again.
By the winter semester of 1918,’lY Roelen had already resumed
his chemical studies at the Technische Hochschule Stuttgart,
where after six semesters. in March 1922. he was awarded a degree.[4’ ‘This was followed by an internship in the iron and steel
industr). spent in the research laboratories of Hoesch in Dortmund. He was apparently unable there to find a suitable topic
for ;I doctoral dissertation, however. and for this reason omitted
all reference to the experience in his later resumes. On the other
hand, Hoesch did make explicit mention of Roelen’s work in the
context of the S0th anniversary of its research division.[51It was
evidently during the course of this internship in Dortmund that
Roelen contacted the director of the KWI regarding the possibil-
Boj. Cornils \\as born in Brenien in 1938. His clzernii.LiI stutlies led to u doctoral degree in inriiistriiil clieniistrj, ( Technisclie Uniwrsitiit Hannover,
1964 1 . He started his cureer at the Ruhrchemie AG
~Ohrrlwuscw)and hecame head of research rind development ( including development of’ biphusic h j s drofOrtnjhtion), before moving to Hoechst AG
(Friinkfiirt) in 1984. His responsibilites have
rritigcti,fioni research to management. Ht, is tlie author of ‘severalpublications on such topics as lzomogerieous anrt ~ieterogeneoirscatalysis, fluorine cliem-
B. Corni’s
ity of pursuing doctoral work at the Institute. In response to the
positive evaluation from Prof. Gutbier cited above. Franr Fischer sent the following note to Otto Roelen:[61
“Herr Professor Gutbier has written to me and expressed the
opinion that you would be in a position to carry out scicntifically worthwhile doctoral studies in one of our areas of research. I am therefore prepared to accept you as a doctoral
candidate. and I request that you meet with me so I can
discuss with you both the topic and the literature that will be
a n essential part of your preparation.”
Since 1921 the KWI had been engaged in intensive invcstigations in the area of gas synthesis, with the goal of producing
liquid hydrocarbons. One of the reasons for this activity was the
fact that Rhineland-Westphalian heavy industries, a source of
financial support for the Institute, were interested in finding
ways of utilizing their excess coke-oven off-gases.[7h1Fischer
and Tropsch were studying as one possible starting point thc
catalytic preparation of “Synthol.” a mixture of liquid hydrocarbon- and oxygen-containing oils described in prewar patents
issued to BASF,[*] and derived from the reaction of carbon
monoxide with hydrogen under high pressure. Much of the ini-
M. Rasch
W. A. Hcrrmann
i.stt.1,. .vjvzthe.res involving carbon monouide, organonirtullic compounds, aspects of cliemical engineering, specialtj. clietniculs, und c o d gasifi‘cution, and /ioIds a number of putcrzis.
A . Herrmatin I ~ U S born in 1948 in Kellieim!Donau (Bavaria J . After studjxing cliemistrj~iDiplonz at the Edini,schc~
C:niversitiit Miinchen) and completing a research thesis with E. 0. Fisclzer in 1971, he obtaitiecl his doctorate in 1973 on ( I topic
cleiiling with orgunometallic stereochemistrj. under H . Brunner at the Universitiit Regensburg. From 1975- 1976 lie c,trrrirtlout
with P. S. SkeN u t tlie Pennsyhaniu State Universitj:, and in 1978 connpleted his lzuhilitation with a c.rztit1erl
Syntlzeses with Diazoalkanes. He was appointed projkssor at the Universitci’t Regensburg ( I 979 J , tind firll
p r o f ~ ~ s s oatr the Universitut Frunkfurt (1982) . In 1985 he accepted a chair at [lie Teclinische C’niversitiit Miinchen ( I S the
.su(’cc’.$sorto E. 0 . Fischer. His area of research i s swthetic. and cutalj,tic chemistry, prinzarilj, in organonnetallic ciieini~strj..Hi]
is tli(>uuthor of350 publicutions, und holds 30 patents. His work has,fri~quentlj~
been tlie subject of special rcJcognition,iiic~luiliiig
tlic Gmnati - French Ale.l-antler-von-Humhol~ltPrize i1988) , tlie Otto-Buyer Prize ( f 990) , and the Mrix-Planck R m w d i
Prize (1991) . He is a member ofthe Akademie der Wissenscliafteri undtler Literatur ;u Main; ( l 9 9 0 J , undreceivediin honorurj.
rioctorate fionz the Universit), of L j m ( I 990) .
Munfietl Ruscli was born in 1955 in Dortniuncl and stiidied histor!, and mathematics c i t the Rulzr- Universitdt B o c h m w i t h the
g o d of‘teucliing in a “G):mnusiuni.” H e spent the years 1984-86 as u teaching intern and n’us suhseywently appointed lo flit’
ricrrrteniic, stuff ut the Mux-Plunck-Institut j i i r Kohlenforscahung at Miilheim un der Rulir where the Director, Prof: Wilkc.
chrrrged hiin until 1992 bvith the responsibilitj, of conducting reseurch on tlu. history of the Institute. He received his rloctorate
( i t Bochum in 1989. and a teaching position at the sume institution in 1990. Since 1992 lie lras been I?ead of the a t d i i v e s lit the
TIiJxcen .4G in Duisburg. In addition to ,four nionograplis he is credited with fist!, other publications related to the liistorj; of’
chiwiistty, .science, and technology as well a.s the application qf computer Irchniques to archival work.
B. Cornils et al.
tial work was directed toward mechanistic aspects of the process
(the “formate theory”). Nevertheless, Fischer and his co-workers failed to develop a satisfactory scientific explanation of the
synthesis. remarking simply in their first publication :r‘)l
reflection and careful observations. I have no doubt that he
will develop into a successful and exceptionally able scientific
colleague. and wish him from my heart all the best for his
long-term future.”
“We wish therefore to conclude this section regarding the
theory of Synthol formation by noting that for the time being
we are giving first priority. relative to other possible explanations. t o the notion of synthesis through carbon monoxide
addition to alcohols. albeit without claiming that we have
definitely proven this to be the mechanism.”
Bucherer was not the only one who regarded Otto Roelen as
an “exceptionally able” chemist: the same was true of the chemistry faculty at the TH Stuttgart, which on the basis of his work
and especially his performance in the oral examination rewarded him with the grade “very good.” Prof. W. Kuster. Roelen’s
adviser in Stuttgart. thereby exceeded Franz Fischer’s recommendation, which attested to work that had been conducted
“with diligence. care. and understanding.” and Roelen’s “full
engagement in the theoretical aspects as well, in the course of
which he developed his own independent views. On the basis of
the results. which represent a considerable advance over prior
knowledge, as well as the way in which Herr Roelen mastered
the problems that developed.” Fischer nevertheless proposed
only a grade of “good.”[I2’ This may have been one reason why
Roelen did not apply for a position at the KWI immediately
upon receiving his doctorate, although the letter of appreciation
he sent to Fischer provides no evidence of ill will between them.
Another possible reason could be that Roelen was interested in
seeking independent appraisal of his research results. Thus, his
dissertation concluded with the following paragraph, appended
quite self-confidently to the bibliography:[’ ’I
I n their explanation of the course of the reaction leading to
Synthol, Fischer and Tropsch assumed that methane and formaldehyde arose a s intermediates. which is the reason why Fischer
et al. (including the young doctoral candidate Otto Roelen; cf.
Fig. 1 ) carried out an extensive series of experiments related to
“The partial combustion of methane to formaldehyde represents a special case in the broad context of gas-phase reactions. one which holds out promise for extensive development
and rich reward from the standpoint of both science and
industry. It is my intention to occupy myself further with
these matters. especially the combustion of methane.”
Fig. I . Otto Roelen (third from left) at the Technische Hochschule
Inor~aiiicL,ihorator>. 1922.
methane combustion and the formation and decomposition of
formaldehyde.”01 Despite these efforts. Fischer and his coworkers never succeeded in detecting more than traces of the
presumed intermediates.[’]
Roelen had completed the experimental part of his work before the institute‘s summer holidays began. and even though his
doctorate had not yet been officially granted he decided to move
on immediately to the Technische Hochschule Berlin-Charlottenburg. where in August 1923 he joined the research group of
Prof. Hans T. Bucherer. He remained in Berlin until March
1924. transcribing during this period his dissertation entitled
“I : Uber die katalytischc Zersetzung des Forniaidehyds bei
hoheren Temperaturen. 11: Uber die teilweise Verbrennung von
Methan 7 u Fornialdehyd mit Luft” ( I : Concerning the Catalytic
Decomposition of Formaldehyde at Higher Temperatures.
11: Concerning the Partial Combustion of Methane to
Formaldehyde with Air). urhich was evaluated very favorably
by Bucherer:“
“The efforts of Dr. Roelen merit special recognition: he has
tried to extract the greatest possible measure of scientific benefit from the investigations he initiated. based on his own
Otto Roelen’s thoughts even a s he worked on his doctorate
apparently were not simply those of a chemist, but of a businessinan as well. On June 10. 1924, he applied for a patent on a
“Verfahren zur Durchfiihrung der teilweisen Verbrennung von
Mcthan zu Formaldehyd” (Process for Accomplishing the Partial Combustion of Methane to Formaldehyde) .[I4’ Objections
were raised to this patent. however, and it was not actually
issued until April 2. 1930. Since it did not even then produce any
financial benefits for Roelen. he abandoned his patent rights in
the very same year.[151
On October 15, 1924, he again took up
research at the KWI for Kohlenforschung. this time as a regular
member of the scientific staff.
Although Otto Roelen was often described as having a “tendency to theorize.” he lacked the publication record that even in
those days was essential to a successful scientist. Thus, during the
period 1924,’25he was a co-author with Tropsch ofthree articles.
all based on his dissertation. but the only independent publication
he was permitted to release was a literature summary under the
title “Uber die Verbrennung von Methan zur Formaldehyd”
(Concerning the Combustion of Methane to Formaldehyde).“h’
This lack of publications cannot be attributed exclusively to the
hierarchical structure of the Institute, which reserved the right
of first publication to the Director. because after 1927 Roelen
served as head of the Institute‘s pilot-plant facilities. with the
rank of group leader. In comparison with other group leaders
. 4 i i ~ c 2 i i C~ ’. l i e i r i .
hi(.Ed Eiigi 1994. 33. 2144 2163
Otto Roelen
his publication record continued to be meager, and was confined almost exclusively to lectures. Roelen was much more
interested in technical issues. of which there were many, because
the Director of the Institute envisioned in-house development of
the KWI-discovered Fischer-Tropsch (FT) process all the way
to technical maturity. In the years that followed, and even during his time as an industrial chemist, Roelen’s list of publications
included considerably more patents than other forms of communication.
Otto Roelen was one of those involved in the initial discovery
of the FT synthesis. During his lifetime he regarded his personal
role in this discovery as having been quite significant, although
the chemical world generally was more inclined to recognize his
contributions to industrial applications of the process.[”’ One
of his contributions, according to his own testimony, was preparation of the technically relevant catalysts. But in the second
published report on the F T process by Fischer and Tropsch,
Roelen is accorded only ii note of appreciation-and even that
in conjunction with references to the work of others as well.[”’
There is no doubt that Otto Roelen played an important part
in the technical development of the F T synthesis. In 1927 he
assumed responsibility for the pilot plant, which was especially
appropriate, since a love for theorizing was accompanied
throughout his life by an interest in practical and technical questions viea.ed from the perspective of an industrial chemist. Many
important innovations associated with industrial implementation of the FT synthesis are attributable to Roelen, including his
”independent temperature controller for a gas-fired oven” and
;I “sulfur determination apparatus” that he developed jointly
with hi5 assistant Walter FeiDt, a device which was subsequently
produced under license by a glassblower in Essen.“”] Tropsch
left the institute in the summer of 1928, and in 1929 FischerTropsch activities at the pilot-plant facility were merged with
those i n the laboratory and placed under Otto Roelen‘s direct
supervision. Thereafter his role in the further development of
the FT process was second only to that of Franz Fischer, who
expressed his confidence in Roelen to the outside world in the
following communication dated March 10, 1931 :I2’]
”With the departure of Dr. Fuchs. our oldest and most senior
chemist, Dr. Roelen. head of the development department.
assumes the duties of proxy for the Director with respect to
general management of the Institute.”
Meanwhile. Roelen and his co-workers in the previously mentioned FT pilot facility (built in 1926) had been working on gas
purification (a constant and virulent problem throughout the
development of the FT process). Other important issues they
nddreswd included the arrangement of the reactors (“catalyst
ovens.” “Kontaktofen” in German; by 1934, 38 different modificationh had been tested). reactor cooling, and temperature
measurement. These experiments are exceptionally well documented. since dl the scientific personnel of the Institute were
required t o submit weekly reports to the Director. Many of the
often hand-written reports have in the meantime disappeared,
as have Roelen‘s originals. But in this context he was quite
cautious: all Roelen’s reports were typed, which permitted him to
retain ;I carbon copy for his personal records. The latter have
since become ;I part of the archives of the Max-Planck-Institut
fur Kohlenforschung, where they constitute an interesting source
of information on technical refinement of the FT synthesis.[”]
Although activities at the KWI pilot plant were centered most
directly on industrial development of the FT synthesis. interesting scientific results were acquired as well. Thus. Roelen discovered in July 1930 that the optimal stoichiometric ratio for
CO:H, was 1 :2.1221The pilot-plant staff also attempted for the
first time in November 1930 to run the F T reaction in the liquid
phase as an elegant approach to solving the problem of adequate cooling. Temperature control was indeed achieved. but
the typical catalysts of that period resulted in a rate of reaction
too low to be practical.[’3i
It was not until the National Socialists seized political power
that industrial-scale implementation of the FT reaction promised
to become a reality. A general license for the process was assigned
to Ruhrchemie AG in Oberhausen-Holten on October 27, 1934.
Quite independently of ongoing licensing negotiations with Franz
Fischer, Ruhrchemie began construction of its own pilot plant.
and acquired from the Institute the services of Otto Roelen to
supervise the work. Roelen was apparently glad to leave the
institute. which had been unable to offer him a permanent position. He had also frequently come into conflict with the authoritarian director as a result of his own unorthodox interpretation
of his responsibility for keeping fixed hours--a situation that
eventually caused problems at Ruhrchemie as well. The agreement Roelen reached with Ruhrchemie on October 23, 1934.
read as foIIows:[”l
“In the pilot plant we have constructed for the preparation of
gasoline according to the Fischer-Tropsch process, you [Otto Roelen] will assume responsibility for managing the fine
purification as well as the actual synthesis itself. including
preparation of the purifying material and the catalysts. and
for managing the laboratory.. . You also have the right and
the responsibility to examine the rest of the pilot plant and
offer suggestions regarding its operation in the interest of
efficient organization.”
In order to adapt existing FT technology to industrial practice. Roelen found himself engaged in problems of gas desulfurization. catalyst preparation and formulation, and the economically important issue of catalyst regeneration. Without the
innovations introduced by Roelen and his co-workers Feiljt and
Heckel it would have been necessary soon to abandon the host
of FT facilities so quickly set up during the mid-1930s. because
at first no method could be found for regenerating the cobalt
catalysts. Roelen and Walter Feiljt ultimately succeeded in dcveloping a catalyst preparation method in which the interfering
impurities were removed by prior precipitation. This process[2s1
and Roelen’s basic patent for the standard magnesium-containing FT catalyst[*”’were implemented at all the FT plants prior
to 1945, and even after 1945 at the Chemische Werke Bergkamen. Many of Roelen’s other discoveries were incorporated alter World War l[ into the South African Sasol facilities. constructed under license from LurgiiRuhrchemie.
Otto Roelen thus served as “chief chemist” for the general
licenser, and as a result ofthe contractually assured exchange of
expertise among the various F T plants he was also among the
best-informed practitioners in the field. Nevertheless. neither he
nor Helmut Pichler, his successor in the Mulheim research group,
was assigned responsibility for the “Reichsamtsversuche” (Official Government Investigations). a set of comparative evaluations of various F T catalysts conducted at the Fischer-- Tropsch
plant in Schwarzheide. This function was instead assumed by
Herbert Kolbel from the FT producer Gewerkschaft RheinpreuBen. Roelen was apparently overburdened with other work.
and also considered an interested party because of his own catalyst-development activities. Moreover. in 1941 he began developing a process for the methanization of carbon monoxide. on
the basis of which a first “gas station” (in the literal sense) was
erected in Essen. to be followed by similar facilities at the Ope1
works in Russelsheim and, after World War 11, in Bochum at the
Carolinengluck mine. in Dusseldorf. and at Rohm & Haas in
When the war ended, Roelen was in Gebhardshagen near
Salzgitter. and at first he managed to avoid questioning by Allied specialists (cf. Section 2.2) by moving out to the farm of
some friends. where he recuperated from an illness. When he
finally returned to Oberhausen in 2945. British military authorities had already learned of his importance and the information
he possessed. On November 4. 1945. the British Ministry of Fuel
and Power ordered his transfer to Wimbledon:[28’
“From the Investigations of the Field Teams in Germany and
from examinations of captured documents it seemed probable that Dr. Otto Roelen had a more complete knowledge of
the research side of the Fischer-Tropsch process than any
other person in Germany.. . Among his own achievements
were the development of the fine-purification process and the
discovery of the ‘ 0 x 0 ’ reaction.”
Upon returning from England Roelen engaged initially in literature work for Ruhrchemie AG and the military government,
pursuing no chemical research whatsoever. Roelen described the
F T synthesis from a historical point of view in the first postwar
edition of G’1limriti.s Eiizj~ltlopdrfierler Trchnisciim CIiemir. This
led to a quarrel with his former colleague at the KWI, Helmut
Pichler, because Roelen’s contribution covered only the “medium-pressure fixed-bed synthesis” as one variant on the FT process, not the “Fischer- Pichler medium-pressure synthesis” (an
expression occasionally utilized by Franz Fischer). which Pichler wished to see treated.[”] After 1949 Roelen became Assistant
Head. and on October 1. 1955, once again Head of the
Ruhrchemie Research Laboratories and Executive Secretary of
the company. He officially retired on March 31, 1962.[291
In the years after his retirement Otto Roelen not only enjoyed
the respect of the scientific community but was also honored
with a number of awards. including the 1963 Adolf-von-Baeyer
Medal from the Gesellschaft Deutscher Chemiker (GDCh) and
the Normann Medal of the Deutsche Gesellschaft fur Fettwissenschaft ( D G F ) (cf. Fig. 2).[291In 1983 on the occasion of
his 86th birthday, and in recognition of his accomplishments in
fundamental processes of coal and petroleum chemistry. he was
awarded an honorary doctorate from the Technische Hochschule Aachen. As early as the end of 1944 he was nominated by
the Ruhrchemie AG for the Dr.-Fritz-Todt prize. However,
since at that time the 0x0 synthesis had not yet achieved any
industrial significance, the responsible authorities declined to
B. Cornils et al.
Fig. 2. Otto Roelen (lell) in 1963 a t the prcaentation of the Norrnann Medal by the
present him with the award, an outcome for which he had every
reason to be grateful in the postwar years.[”]
Apart from this. Roelen’s retirement years were devoted to his
numerous hobbies. Many of these he had taken up earlier, as is
evident from a close scrutiny of his publications and his personal
papers from his years at the KWI and Ruhrchemie. He eventually found the leisure necessary to prepare comprehensive articles describing his contributions to the 0 x 0 and
~ ~Fischer~ ~
Tropsch 11 7 . 2 21 syntheses, in which he laid considerable stress
on those aspects relevant to the history of chemistry. All
three papers are exceedingly informative, because he was able to
write them not only as one of the direct participants, but also
with perspective acquired after four decades. analogous to
G. Schiemann’s situation as he looked back over the field of
fluorine chemistry (cf. Fig. 3). .
Fig. 3 . Friendly exchange between two chemists for whom reactions were named
G. Schicniann (1899- 1967. the Schicmann reaction for fluorination ofarenes) and
0. Roelcn (1897-1993) in conversation a t the bowling alley (.‘Kcgelhahi17 ol‘thc
Ruhrchemie AG: photo taken July 23. 1964.
Another important issue for Roelen was his personal health.
with which he conducted systematic experiments. It was this
period of experimentation that led to an article entitled “Behandlung der Luftwege mit angereicherten Meersalz-Aerosolen” (Treatment of the Respiratory Tract with Enriched Sea-Salt
Otto Roelen
Aerosols) ,[331 in which he provided experimental details regarding what was apparently a very positive set of experiences,
extending even to the question of the most appropriate materials
for constructing an inhaler. Roelen was particularly intensively
engaged with questions of the relationship between nourishment
and one’s state of health, occasionally displaying the zeal of a true
missionary. This led to a number of short manuscripts[34.351 as
well as papers and personal experiments on the subject of allergens.‘”’
Roelen shared with the great chemist William Crookes (18321919). inventor of the crookes tube for investigating cathode
rays. an inclination toward questions that would typically be
regarded LLSthe exclusive domain of parapsychology.[371Whereas Crookes pursued the occult and nurtured a “familiar relationship with ’materialized personalities’,” Otto Roelen spent
his time in the “shadow world between the known and the
searching for quantifiable experimental verification of oscillation phenomena, whose “objectification” he felt
always on the verge of achieving until a stroke in 1981 prevented
him from pursuing further experimental work and applying his
recently acquired extensive knowledge of electronics and semiconductors. His typewritten manuscript on questions relevant
describes his experiments in detail, with photographic documentation of his experimental setup and an account of results he acquired in the 3.1 8-cm wavelength range.
But it also conveys his singular conviction that “oscillatory perception.” like color blindness, is confined to only a minority of
sensitized individuals. In sharp contrast to his attitudes in many
other respects, he concluded the 1980 typescript with the resigned observation: “Much that is observed for the first time
remains inexplicable..
But his greatest academic obsession during retirement was a
lively interest in historical and didactic problems related to research, probably stimulated in part by his excellent insight into
his own discovery of the 0x0 synthesis and his deep disappointment for having failed to recognize the true nature of the catalysis involved (Section 3.2). A study by Roelen dated as early as
1968 and entitled “Emotik- Von den iiberzeugungen und ihren
heimlichen Herrschern”[391(“Emotik”-~ Convictions and Their
Secret Masters) explores the contrasts between opinions and
convictions, considering their rational and emotional content as
well as their treatment by natural scientists in light of the
methodological skepticism expressed by Descartes. The motif of
“semantic deception” on the part of nonscientists appears at a
very early date as well; indeed. it is little wonder that in his circle
of friends he came to be known as an evangelist on behalf of
C. P. Snow,‘“”’ who began in 1959 to call attention to fundamental incompatibilities between the pronouncements and
worldviews of scientists and those of humanists (“The Two Cultures.”[”’ still referred to euphemistically as “literate circles”).
Roelen concluded in 1968 that
“this cultural dilemma. . . exposed by Snow is so alarming
precisely because those with a humanistic education-who
persist in their denial, ignorance, and misunderstanding of
the achievements of science~-are the very ones occupying the
seats of power.”
The symptoms and consequences of this cultural dilemma can
be formulated earnestly,[42.4 3 1
or in a martial spir-
it, the latter illustrated by Roelen’s 1983 response to the question
of how scientific discoveries come about :I4’)
“A further example of the way research is hampered by the
spirit of the times is presented by the attack on science and
technology. . . The demand is made that scientific research . . .
should assume a set of moral obligations, and subject itself to
social planning. This has been very clearly expressed. for example. in concepts developed at the former Max-Planck-lnstitut in Starnberg for the culmination of the sciences.
“Such demands are advanced by people who have never
engaged in experimental research, and who are able to maintain their positions only by semantic blurring and factual
errors.. . .
2. His Greatest Achievement: The 0 x 0 Synthesis
2.1. History of the Discovery
It WAS in 1934 that Roelen moved to the Ruhrchemie AG. and
it marked a turning point in his life. Adolf Hitler’s Third Reich
was aiming its sights quite openly and single-mindedly toward
military conflict with Germany’s neighbors. Military preparations quickly involved the chemical industry, including Ruhrchemie. whose fertilizer business had become increasingly unprofitable following collapse of the international cartel negotiations
coupled with the compulsory cartel and international trade restrictions imposed by the German nitrogen syndicate and nggressive quota politics on the part of the I. G. Farbenindustrie
(I. G.) conglomerate.[461All of this had affected Ruhrchemie in
one way o r another.
One possibility for escaping the desolate economic situation
called for broadening the company’s product spectrum, which
led to efforts directed toward coal chemistry (niethanization,
methane cracking to yield benzene or acetylene), as well as an
increase in activity at the Chemische Fabrik Holten GmbH,
which had been established in 1929. The latter originated as it
joint venture operated by Ruhrchemie AG and the Th. GoldSchmidt AG in Essen for preparing glycol from ethylene isolated
from coke-oven gas. Even as the plant was being built, thc
market leader in this sector, I. G . Farben, insisted on becoming
involved financially in the new operation and playing a significant role in marketing. demands that were in Fact met. This
serves as yet another example of the way I. G . insinuated itself
into the plans of outside concerns. just as it had in the disputes
related to fertilizers. Persistent interference of this type was one
of the constant factors over it period of many years that marked
the tense relationship linking Ruhrchemie and Otto Roelen himself with I. G . Farben and its chemists. Attempts are still being
made to this day by I. G. apologists to rewrite history in such a
way as to gloss over the picture of this domineering. no-holdsbarred monopolizer.[46]
One potentially promising foothold for Ruhrchemie was the
Fischer-Tropsch synthesis (cf. Section 1). Following preliminary negotiations and attempts by I. G. to limit competition
with its own fuel production based on coal hydrogenation. Ruhrchemie acquired the rights to the FT process as general licensee.
which entailed the obligation to pursue development ofthe tech2149
nology to the point of constructing a demonstration facility and
a pilot plant capable of producing 5000 t ~ a . [ ~ ’ ~
Otto Roelen was thus fully aware of what awaited him a s lie,
his colleague Dr. Feint, and his chief technician Hanisch made
the move in 1934 from the KWI in Miilheim to the Ruhrchemie
works in nearby Holten. a suburb of the city of Oberhausen.
And he was also well prepared. As head of the FT demonstration facility at the KWI he was effectively predestined to undertake this assignment and assume the responsibility for FischerTropsch development efforts at Ruhrchemie. The Ruhrchemie
organizational plan during the period 1934- 1945 as presented
in BIOS Report 447[’*] indicates that Roelen’s F T research activities were initially transferred from Ruhrchemie itself to the
sister corporation Ruhrben~in.‘~’]and then back again to
Ruhrchemie. This plan also documents a deliberate policy (for
reasons of secrecy) of mutual isolation of all the various research
facilities. a policy basically consistent with Roelen‘s own temperament. but which nonetheless hindered the constructive exchange of ideas. Even BIOS Report 447 contains disparaging
remarks with regard to this organizational structure.[”I
The emphasis in Roelen’s work with Ruhrchemie was still on
the continued development of the FT synthesis in 1938, when
seven FT plants were either already in operation or on the verge
of starting production. The general licenser was compelled to
deal with a great many questions during the construction and
early operational phases of these new facilities, most of which
became the responsibility of Roelen’s department-often without preliminary screening or prioritization. This work load was
augmented by the obligation to certify all F T catalyst charges
and the additional burden of a laborious and time-consuming
search for a substitute for cobalt, a stratcgically important and
exceedingly costly metal that served a s the basis for F T catalysts. The latter problem was made all the more troublesome by
the fact that it necessarily entailed very prolonged test cycles.
One particularly urgent aspect of FT studies at that time concerned attempts to recycle “gasol” hydrocarbons (C,-C, compounds. including olefins and especially ethylene)[481a s a way of
incorporating them into higher hydrocarbons. In contrast to
later research on “selective FT synthesis,”r49’ethylene was completely useless for gasoline synthesis. Based on agreements between the licensees. and as part of an official exchange of information. attempts were to be made to ascertain whether and to
what extent it was feasible to incorporate lower olefins into the
product through recycling. and whether NH, might also be
suitable for inclusion in a ”growing F T chain.”
At the end of 1937 in the course of these investigations Roelen
discovered the aldehyde synthesis that was later to bear his
name (the Roelen reaction, hydroformylation, 0x0 synthesis).
The actual discovery was a direct consequence of problems encountered with two atmospheric-pressure FT ovens, one of which
had been charged with ethylene and the other with ammonia,
ovens that were connected for waste-disposal purposes by a common off-gas pipe (for complete details see ref. [32]).In the course
of this particular experiment a white residue accumulated in the
piping, the odor of which was reminiscent of aldehyde-ammonia
compounds (specifically the aldimine derived from ammonia and
propionaldehyde. where the latter had arisen from the reaction of
ethylene with synthesis gas). This observation set Roelen on the
trail of the 0x0 synthesis. Experiments designed to establish
21 50
B. Cornils et al.
optimal reactions conditions and the overall potential of the
reaction were resumed on July 26,1938, as soon as the appropriate pressure equipment had been acquired. Intensive investigations followed. and by September 20.1938. the first patent application on the 0x0 synthesis was filed. Finally on June 17. 1952,
a patent was issued with the number 849548[”’ (Fig. 4) covering the following claims:
“Procedure for the preparation of oxygen-containing compounds in which unsaturated hydrocarbons (e.g., olefinic hydrocarbons) are treated at elevated pressure and temperatures up to approximately 200 ‘C with water gas or other gas
mixtures containing carbon monoxide and hydrogen.”
Fig. 3. k-acsimile of the first
patcnr from 1938,1952 [50]
In a retrospective paper describing the discovery of the 0x0
synthesis, prepared in 1977 and entitled “Beitrag zur Psychologie
der naturwissenschaftlichen Forschung” (Contribution to the
Psychology of Scientific Research), Roelen provided a lengthy
case history of this exceptional chapter “in the larger context of
the catalytic reduction of carbon
the description he furnished in 1946 for BIOS Report 447IZ8]is
identical in content.) Roelen includes in this case history experiments undertaken at BASF in 1913, in which higher hydrocarbons and oxygen-containing compounds were first formed catalytically from CO and Hzat elevated pressures.[81Fischer and
Tropsch (later Roelen as well) used these experiments as their
starting point in 1922 and thereafter at what was then the KWI
Otto Roelen
(today the Max-Planck-lnstitut) in Miilheim when they utilized
iron catalysts to prepare “Synthol.” a mixture of oxygen-containing compounds. These later experiments were conducted at
quite high pressures. The more active the catalyst, the lower the
required pressure. and the more the nature of the product shifted in the direction of hydrocarbons, an observation that led
ultimately to discovery of the atmospheric-pressure Fischer
Tropsch synthesis (cf. Section
Quite independently of Fischer’s experiments, Smith, Hawk,
and G ~ l d e n [ ~at- the
~ ] United States Bureau of Mines had also
attempted to introduce ethylene into the reactant stream in an
atmospheric-pressure FT reaction over a cobalt catalyst. With
the exception of high pressure, all the essential conditions were
thus established for the subsequently discovered 0x0 synthesis.
(FIAT Report No. 1000 actually describes parenthetically -and
quite incorrectly- the paper by Smith et al. as the “first publication of the basic 0 x 0 reaction.”[s41presumably in reaction to
claims of success arising out of the Third Reich.) Smith, Hawk,
and Golden did indeed obtain some aldehydes and alcohols, but
they interpreted them explicitly to be intermediates produced in
the course of the FT reaction. Roelen formulated the matter
rather more logically when he asserted
“the cited Americans did indeed carry out the aldehyde synthesis in 1930. but they did not discover it. Their presuppositions with respect to the reaction mechanism prevented them
from recognizing that a second. independent reaction was
involved. This intellectual inhibition was confirmed for the
author orally in the course of a later visit.”
Intellectual inhibitions and presuppositions regarding the nature of the catalysis played a role in the later history of the 0x0
synthesis as well (cf. Section 3.2). Thus, because of the “general
impression of the experts that oxygen-containing by-products of
the F T synthesis were inevitably and inseparably related to the
mechanism of hydrocarbon
an independent synthesis of oxygen-containing products was never even considered. This is confirmed by widespread acceptance of the Synthol
(I. G . Farbe~iindustrie[’~])
and Oxyl (Ruhrchemie AG[48,56. 5 7 1 )
syntheses as variants of the FT synthesis.
Thus. in 1937138 Roelen’s real intellectual accomplishment in
analyzing the operational disruption described above was freeing himself from any preconception about oxygen-containing
compounds and their inevitable appearance as intermediates
in a normal F T hydrocarbon synthesis. Perhaps most important, the absence of a typical series of compounds with increasing molecular mass led him to suspect the existence of an independent synthesis of propionaldehyde [Eq. (a)] and diethyl
ketone based on ethylene that had been introduced into the
He concluded that such a reaction, if it occurred. must be dependent on pressure, and that propionaldehyde
formation would be favored by an increase in pressure. The first
high-pressure 0x0 reaction (243 CjlOO bar) was conducted on
July 26. 1938. and it confirmed Roelen’s suspicions. Subsequent
process optimization for the 0 x 0 reaction involved parameters
clearly outside the range appropriate for an FT reaction, in-
cluding relatively low temperature and high CO/Hz pressure.
Shortly thereafter studies were initiated on possible applications
of the new synthesis, and patent protection was sought as outlined previously.
The term “oxo” as applied to this reaction was coined by the
Ruhrchemie patent department, and was intended to suggest a
general reaction for the synthesis of both aldehydes ~ i i 7 dketones
(i.e., 0x0 compounds). although it was later established that this
flexibility is limited to ethylene. The “invention” itself was noteworthy from one additional standpoint: a German patent was
never actually issued until July 1952. and then on the basis of the
Patent Transition Law (“Patentuberleitungsgesetz”) of the Federal Republic of Germany, whereas French, Italian, and Ainerican versions appeared (but attracted little notice) during World
591 The war itself had the effect of depriving Roelen of
the international monetary fruits of his discovery. because all
foreign patent rights assigned to Gerinans were confiscated after
the war. As a result Roelen and Ruhrchemie received royalty
payments only from the German 0x0 facilities operated by
BASF and Hiils, not from the much larger forcign produccrs.
It should be noted in passing that the discovery of the 0x0
synthesis is still controversial; experience has shown that successful children are frequently claimed by multiple fathers. In
discussing the matter, Roelen always emphasized the Fact, underscored in his retrospective description of the discovery, that
the definitive experiments were carried out at his own risk, and
that their further pursuit was against the express wishes of company
“Thereafter experiments on the effect of synthesis-gas supplements were abandoned at the instruction of the management.”
That was in December 1937; based on the considerations described above, Roelen modified the experimental protocol between January and June of 1938 in such a way that it was possible
for a first successful high-pressure experiment to be carried out
on July 26. 1938.
As usual, management saw things in a somewhat different
light. In the “Minutes of a Presidia1 and Executive Board Meeting of the Ruhrchemie and Ruhrbenzin Aktiengesellsch a ft on
February 6. 1940”[h01remarks on the subject of fatty alcohols
by F. Martin. at that time Chairman of the Board of both
Ruhrchemie and Ruhrbenzin,[611are recorded as follows:
“Martin sketched out the history of the development of the
process for preparing aldehydes and fatty alcohols. Concerns related to the disposal of relatively large quantities of
gasols derived from fuel synthesis, materials with only ;t limited potential for exploitation, had induced him to direct Dr.
Roelen to undertake experiments into the possibility of utilizing these gases for further reaction with water gas. I t was
found that the olefins could in fact be converted into
straight-chain and isoaldehydes . . . .”
Martin told the same story during the first round of questioning by C. C. Hall’s CIOS team, who reported as follows: ”In the
gasol fraction, they had large amounts of propene and butene
for which they had no use, so Martin instructed his chemists to
find some more use for these compound^."^"^^
21 51
In other words, the Executive Board had its own interpretation. at least with respect to causation in the history of the
discovery. It is safe to assume that Otto Roelen was not aware
of the corresponding minutes. which during the war were declared to be “confidential” (and that he never saw them after the
war since he was not a member of the Executive Board). Thus,
it is all the more noteworthy that he continued to insist on the
role played by successful insubordination--not the last time,
incidentally. that insubordination was to have a place in
Ruhrchemie‘s history of the 0x0 synthesis.
B. Coi-ids et al.
nomic politics of the National Socialists, so much so that it
quickly attracted the greedy attention of others. The first entry
dealing with Roelen’s discoveries in the minutes of the Executive Board of Ruhrchemie is the above-cited account by
Martin regarding the history of the matter.lholThe record continues as follows:
“At the instigation of the government it is now likely that
together with I. G. and Henkel we will construct a synthesis
facility with a capacity of 120000 t/a in Upper Silesia . . . It is
further anticipated that Ruhrchemie’s share of the investment will somehow take the form of a licensing agreement. . .
Martin noted in addition that prior to approaching Henkel
and I. G. it would also be advisable to confer with GoldSchmidt . . . .”
2.2. The Industrial 0 x 0 Synthesis during the Early Years
The 0x0 synthesis was an excellent match for the raw materials accessible to the Ruhrchemie AG, which had FischerTropsch facilities as a source of olefins, experience in catalyst
preparation, and water-gas generators (cf. Figs. 5 and 6[1241).
The 0x0 synthesis was also well suited to the war-oriented eco-
Ruhrchemie and I. G. then jointly established the Chemische
Verwertungsgesellschaft Oberhausen mbH, a corporation that
assumed all rights related to the 0x0 process and was prepared to grant licenses. The nature of further interaction with
Henkel and I. G. was spelled out in detail in a meeting of the
Executive Board on July 4, 1940.L”21
Another company, the
Oxogesellschaft mbH. controlled equally by Ruhrchemie,
Henkel, and I. G..[631was expected to erect a 15000 tia facility
for the production of synthetic fatty alcohols. whereby
“further processing of crude intermediates to finished products by the company itself [i.e., Ruhrchemie; clarification by
the authors] is out of the question. since in accordance with
the government’s wishes facilities belonging to Henkel and
I. G. have been set aside for this purpose.”
Fig. 5 . The clc\wi water-gas generators used to supply the Fischer-Tropsch facilities a t Ruhrchemie (1941)
The extent to which .‘the government‘s wishes’’ were actually
a reflection of influential guidance of I. G. can only be a matter
of speculation today. Interestingly. this joint venture between
Ruhrchemie and I. G. was later interpreted as Ruhrchemie’s
admission of parallel discovery of the 0x0 synthesis by I. G. :[h41
“Comme, d‘autre part, 1‘1. G. Farbenindustrie de Ludwigshafen avait elle aussi trouve independamment cette reaction, un accord est intervenu entre la Ruhr-Chemie et
1’1. G.”[*]
This interpretation, which is contradicted by the facts, is presumably related to a similarly incorrect report issued by the U.S.
Naval Technical Mission in Europe;[’381there is no proof to
substantiate it. and it has found no backers despite efforts in
that direction. For example, the 0x0 synthesis as defined above
has sometimes (not surprisingly) been attributed to Reppe, as a
special case of the “. . . general group of reactions between
olefins, carbon monoxide and additional compounds such a s . . .
and H, . . .”[541 investigated and claimed by him, and it has
occasionally been peddled as such by Reppe and his disciples.[651
Interestingly, BIOS Reports 273 and 355, which are dedicated
more directly to Reppe, d o make mention of the 0x0 synthesis
(indeed, with [Ni(CO),] as catalyst!) but without naming Otto
Roelen.[’ 1 9 ]
Fig. 6 Atmobpheric-pressure Fischer- Tropsch reactor at the Ruhrchemie plant
(IcTt). with the besscl used for introducing a catalysc charge (1942)
“Since I G. Farbeiiindustrie also discovered this reaction independently. a n
agreement was arranged between Ruhrcheinie and I. G ‘’
AnRew. C‘hem. hii.E d Dig/. 1994. 33. 2144 2163
Otto Roelen
Although Board Member Kost (General Director of the Ruhrchemie Shareholders, Gewerkschaft Rheinpreussen) correctly
noted during the meeting of the Executive Board that the
planned venture “was not consistent with the concept that led to
the formation of Ruhrchemie and Ruhrbenzin”-namely
production of chemicals independently of I. G.[47]-his opposition proved futile. Kost nevertheless ensured that his reservations would be expressed very clearly in the
“Today’s events are another example of I . G.’s efforts to buy
up the primary products of the Fischer synthesis and thereby
prevent the companies [e.g.. Ruhrchemie; clarification by
the authors] from participating in the profits derived from
In this way Ruhrchemie AG was once again prevented from
gaining direct access to the market.
On November 13, 1940, the Executive Board of Ruhrchemie
resolved to construct a facility for producing 7000 tja of fatty
alcohols; Henkel was to assume Ruhrchemie’s portion of the
construction costs.[6”’ A year later the 0x0 facility was under
construction,[”] after Oxogesellschaft mbHL631
on February 28,
1941. issued a construction order to Ruhrchemie on behalf of its
three partners (Ruhrchemie, BASF, and Henkel) to establish a
‘.facility i n which ca. 10000 t/a of olefins with a chain length of
C , I C , are to be converted by the 0x0 process into fatty alcohols or fatty acids”[h81-and thus into detergents. Because the
relevant minutes of the meeting of the Executive Board are no
longer availablc (presumably as a consequence of the war), it is
impossible to reconstruct a complete chronology of this first commercial application of the 0x0 synthesis (cf. Figs. 7 and 8). It is
Fig. 7 Ruhrcheniie
facilit). shown under coiistruction (1943)
clear. however. that with the exception of tests related to some
of the components, the facility itself was never in operation
during the war years,[““] perhaps in part because I. G . was able,
upon payment of licensing fees. to test the available Ruhrchemie
know-how directly in its own pilot facilities. With up to 100 tons
per month of its own oxoalcohols produced in this way,
1. G. h a d little further interest in a plant not under its direct
The Chemische Verwertungsgesellschaft Ober-
Fig. 8 Distillation facililirs and administration building of the 0 x 0 GinbH
hausen mbH, charged with ‘*theexploitation of chemical processes [and] the projection of fxilities for licensees . . .”.[6“1 was
not dissolved until 1973,”OI serving into the 1950s a s patent
applicant on behalf of both Ruhrchemie and BASF with respect
to inventions relevant to the 0x0 process.
FIAT Report 1000[5”1provides a wealth of interesting information (which would otherwise have been lost) regarding the development of the 0x0 process during the war. Otto Roelen’s attention in Oberhausen-Holten was concentrated on the preparation
of higher fatty alcohols intended for conversion into detergents
and soaps.“’“] I. G. had no access to FT olefins, and therefore
devoted its efforts exclusively to the utilization of lower olefins
(C, -C,,,) and the production of plasticizers of the palatinol
type, as well as the further utilization of lower aldehydes (c.g..
in perfumes: cf. references to Reppe in ref. [38]).
Ruhrchemie’s first 0x0 facility consisted of a “prcfractionator”
for the starting olefins. 0x0 and hydrogenation stages. a filtration
system, and final distillation towers (cf. also refs. [54, 711). The
FIAT report actually contains the first use of the English expression “to oxonate,” intended as a counterpart to the German
L.oxieren”; [ 7 4 the latter was an unfortunate piece of terminology
invented by the Ruhrchemie patent department, which only later replaced it by the more correct “HydroformyIier~ing”[’~~
(hydroformylation) and the alternatives “Roelen Synthesis“ (proposed by Hall in 19461741)and “Roelen Reaction (Adkins,
Nevertheless, the term “oxieren” continues to be part
of the technical vocabulary at 0x0 facilities operated by HASF
and Ruhrchemie; even semiotic heresy can prove to be surprisingly persistent!
The flow sheet reproduced in Figure 9 provides details concerning the first 0x0 facility constructed by Ruhrchemie in
Holten. The reaction was to be carried o u t in batch mode at
135 C and a pressure of 200 bar. Plans called for using a standard FT catalyst consisting of cobalt. thorium oxide. magnesium oxide, and kieselguhr in a 100:5:8:200 ratio. to be introduced as a suspension (slurry) that would subsequently be ground
together with the olefin. After transfer to 3 second reactor and
purging of the gas, crude 0x0 product was to be hydrogenated
in a single phase over the same catalyst. leading to the desired
fatty alcohols. Preliminary experiments indicated a probable
catalyst consumption of roughly 300 kg per day, primarily be21 53
B. Cornils et al.
cause of heavy catalyst losses accompanying post-hydrogenation separation on the ceramic filter. Extensive investigations
indicated that the preferred construction material was 310.5 %
chromium-molybdenum steel, a difficult item to procure in
those days. The now cobalt-free reaction product was to be
fractionally distilled in a final purification step. The projected
average yield was 80%; 20 YOof the starting olefin was expected
to be converted into a high-boiling fraction (referred to by the
CIOS team as “thick oils.” a literal translation of the German
”Dick61e”[l 241), consisting primarily of aldols. I t was thought
that these could be largely hydrogenated to the corresponding
alcohols (including 2-ethylhexanol[‘ 241).
In keeping with the “oxo agreement” that had been concluded with Ruhrchemie. other 0x0 pilot plants were to be established at I . G. plants in Leuna. Ludwigshafen, and Oppau. Instead of Roelen’s batch procedure these plants were designed for
continuous fixed-bed and slurry processes; carrier-free cobalt
catalysts (e.g.. cobalt naphthenate or acetate) were added subsequently to make up for cobalt losses (for details on the equipment and the corresponding engineering see ref. [54]). A remarkable number of the engineering and equipment features
found in the Oberhausen and I . G. facilities were incorporated
into later industrial 0x0 plants. including the cooling systems
I ?
(liquid or gas). gas circulation schemes, grinding and introduction of suspended catalysts, pressure filtration of the pyrophoric
catalysts. pumped transport of suspended catalysts. and carbony1 generators.
The first 0 x 0 facility constructed under license was destined
for the explosives manufacturer Bombrini -Parodi-Delfino in
Col1eferro;Ronie. Plans called for the conversion of ethylene
into 25-30 tons per month of propionaldehyde. which was then
to be reacted with formaldehyde to give trimethylolethane
(TM E. 3-hydroxymethyl-2-methyl-I 2-propanediol), a potential substitute for the important explosives intermediate pentaerythritol. This tacility was designed for continuous production with a suspended catalyst (FT catalyst. suspended in diesel
oil). but by the time the war ended only the corresponding
reactor had been sent from Holten to
related to the conversion of propionaldehyde to TME had been
entrusted to G. Natta, among others,[”l which explains Natta’s
early familiarity with the 0 x 0 synthesis (and his acquaintance
with the Chairman of the Board of Ruhrchemie. F. Martin”’]).
The work in Holten and at the I. G. plants led not only to
valuable engineering data, it also shed light on a number of fundamental chemical principles,[28. s4. ”. ’‘I some of which were
later “rediscovered” by others. This is the case. for example.
010 G L s E w m r T m n WWCOYN
HOCTEN W 110 )u( 4011
DATE FEE 24,1947
Fig. 9 . Schematic diagram (flo%slicet) of the
21 54
0 x 0 facilily .iL Holten (Fig. 1 i n
ref. (541)
A n y w . Clwtir. / f i r . E d EnxI. 1994. 33, 2144-2163
Otto Roelen
with what has come to be known as “Keuleman’s rule,”[781
according to which steric and electronic factors ensure that hydroformylation of isobutene will produce almost exclusively 3methylbutanal. a phenomenon already observed by both I. G.
and BASF‘’”] as well as Roelen himself,[80,‘11 and communicated
in the FIAT report[541(cf. also ref. [64]).
The reports o f t h e Allied commissions of inquiry (e.g., BIOS,
CIOS, and FIAT) make unusually fascinating reading even today.[”] These special units consisting of outstanding specialists
from science and industry followed on the heels of the troops.
Their assignment was to provide the respective countries (and.
less explicitly, individual firms) with information on German
scientific and technological progress during the war years, as
well as insight into the current level of German know-how. It is
also important to recognize in this context that at least the
American FIAT teams-consisting of 6 000 experts assigned exclusivelj to an investigation of the German chemical industry-were granted extraordinarily comprehensive powers, including
the right (in the true spirit of the late James Bond) “to remove.
arrest, and intern individual Germans.’””, 1 2 2 .
The discrepancy between official instructions from the government and personal obligations to .individual firms made it
easier for many of those questioned to limit the amount of
information they provided, and in some cases even to introduce
obstacles. A striking example is Otto Roelen’s behavior with
respect to the Farragher Report on Fischer-Tropsch research at
Ruhrchemie. prepared in 1947 by Warren F. Farragher (who
had already served as co-author of the CIOS report covering the
entire Oberhausen facility[571).Farragher was employed by the
Houdry Process Corp. in Philadelphia. His report was to be
based on testimony from various German experts, and was allegedly for the United States
Otto Roelen had
given the impression that he was quite willing to provide information during his questioning from November 1945 to Septernber 1946 as a civil intern in Wimbledon, although he himself
always regarded this period as one of defamatory “imprisonment” (cf. Fig.
With respect to Farragher’s demands,
however, he was utterly intractable. The events leading up to the
Fig. 10 Otto Roelen as a civil intern at the Beltane School. Wimbledon, 1945:46.
.4t7~Tml’.(‘Iw~n.1t7l. Ed. E~7,yl 1994. 33. 7144-2163
report were described by Roelen in the preface to his own account as foIIows:[831
“As former head of the research laboratory I was assigned
the task of preparing a report on Ruhrchemie. Owing to my
imprisonment in London, I was a very familiar figure at the
relevant British office in Dusseldorf. There I learned that the
Farragher operation was i n no sense being conducted under
orders from the occupation forces, but amounted instead to
a private effort on behalf of American industry. In view of
this situation I did indeed undertake and in fact complete the
requested Ruhrchemie report, but in spite of an anticipated
and delivered scolding, I did not submit it punctually. As a
result, Mr. Farragher returned to the United States with
eight Fischer-Tropsch reports.. ., but not with one from
Ruhrchemie . . . For this reason the contents of the
Ruhrchemie report have remained largely unknown.”
Moreover. Ruhrchemie refused even a t a later date to permit
cost-per distribution of the report, and after the currency re-
form (1948) it enlisted the Economics Ministry of the State of
North Rhine-Westphalia in support of its position relative to
Farragher when the latter returned to Europe in 1950/51.’471
Only through Roelen’s preface, cited above, did the whole process-described with revealing openness by Gimbel[”] as wellbecome fully understandable (cf. Fig. 11).
Fig. 11. Otto Roelen in Oberhauseii a t the time the Farragher Report was preparcd
(1947). shown here with his legcndary bricfcaye.
The opinions reflected in the Allied reports with respect to
new and, from their perspective, previously unknown developments such as the 0x0 synthesis were somewhat mixed. The
reports remain a fundamentally sound source of insight into the
state of technology in 1945 (albeit with occasional ambiguities
as a result of misunderstandings). The quality of thc information is of course a function of the competence of the particular
investigators involved. Thus. reports on the 0x0 synthesis are
quite varied, depending on whether they were prepared by the
two-man teams Hasche;Boundy[”I and Withers,”est,[“8’ or
one of the groups associated with Farragher,[”]
(cf. Fig. 12). Some of the inquisitors made liberal use
B. Cornils et al.
plications. this publication cannot be held to give any protection against action for infringement.”
This statement was rarely extended by “andior US
Patents.”[8JJ and never adapted to cover patent rights of the
other victorious powers--clear indication in whose interest the
interrogations were actually conducted. It is therefore not s i r
prising that 0x0 facilities in the United States benefited.[8s1Contemporary press reports announcing the opening of new plants
often ignored the country of origin for the process. and almost
never mentioned the name Roelen. France was in this respect an
exception. 0 x 0 developments there were greatly influenced by a
former Ruhrchemie employee, Lemke. who had worked in
Oberhausen from 1941 until 1945.[861
Economic data in the Allied reports is also interesting. During
his interrogation Otto Roelen expressed himself in very vague
terms: [“I
“Finally Roelen said that he did not know if the 0x0-process
would be an economic proposition in peace time, hut it was
possible that it would, since Germany had to import large
quantities of natural oils for production of soap and detergent s.‘’
Fig. 12. Discussion of the FIAT Reports at the Martin family‘s gardcn house in
Mulhcim-Ulilenhorst. April 1Y47 (Crom the left: Rosendahl. Weinrotter ( K W I
Mulheim). Cehrke. Martin. Roelen (all three from thc Ruhrchenire AG). Koch
(KWI)]: photo takcn by M r Atwell. FIAT]
of information from the interviews in their own publications,
adding critical commentary on the historical development of the
0x0 reaction-from the British perspective, for example- and
showing no hesitancy when it came to value judgments (cf.
for example. who published a somewhat embellished version of his CIOS report^^"^). All the reports are tainted
with at least a whiff of industrial espionage-quite understandably. given the history of the Third Reich; this was regarded by
the British, for example, as a form of “hidden reparations” and
compensation “. . . not only in direct damage, but in loss of time
for research and re-equipment . . . . ” [ 1 2 3 1 The expropriation of all
foreign patent rights, which was very painful and also financially devastating for the victims (including Otto Roelen), had deprived both the discoverers and their companies of the fruits of
their labor. The following opening comment from the reports is
thus especially moving to read:[”]
“This report is issued with the warning that, if the subject
matter should be protected by British Patents or Patent ap21 56
Economic calculations, presumably based on a merger of the
National Socialist wartime and self-sustaining economic projections with those drawn up by the Military High Command (and
therefore not very reliable), estimated for the preparation of
100 kg of fatty alcohols a cost of 78 Reichsmark (RM) (for the
Oberhausen facility, with a capacity of 12000 t.’aIS7,1241): the
cost under continuous operation was expected to fall to ca.
60 RM per 100 kg. assuming an olefin price of 45 RM per 100 kg.
For comparison, the cost of primary FT product was estimated
at roughly 24 RM per 100 kg (Bergkamen facility. 1944[’“]).
A few additional comments are in order with respect to the
subsequent history of the first 0x0 plant, that at OberhausenHolten. Activity here during the war was limited to the testing
of a few of the individual components, and orderly production
was ncver achieved. The facility w a s damaged during the final
months of the war. but not so severely that its rcsurrection
would have been impossible, or possible only at unreasonable
Thus. the struggle to retain the 0x0 plant, along with
an attempt to prevent demolition of the largely destroyed FT
facility. was a life-and-death matter for Ruhrchemie in the immediate postwar years. I t was argued for example, that the 0x0
plant was needed to guarantee the hygiene and health of an
undernourished population. which was living under a threat of
epidemics and hence in need of a reliable source of soap and
cleansing agents based on synthetic fatty alcohols. In other attempts to stall demolition of the 0x0 facility Ruhrchemie accepted a foreign partner (the Sunlicht subsidiary of Unilever) in the
0 x 0 GmbH, and worked on negotiation of a contract with the
British concern Balduin, which (because it belonged to the Allies) might have offered some protection in the interest of acquiring detergent alcohols for its own purposes from the 0 x 0
Nothing helped. however. By 1950. one of the two production
lines of the 0x0 plant had been dismantled (Fig. 1 3 t o n l y to be
reconstructed at considerable expense starting in 1951. Never
Otto Roelen
success story was due in large measure to efforts of the
Ruhrchemie engineering department, but Otto Roclen’s research again played an important role.[891
Several observations dating back to the war years were clearly
suggestive of the true nature of the catalysis (homogeneous),the
catalytically active species (tetracarbonylhydridocobalt) . and at
least parts of the reaction mechanism. The initially inexplicable
and troublesome loss of cobalt through soluble cobalt compounds,[’*’ the pyrophoric nature of the catalyst.‘5“’ and thc
elegant utilization of cobalt carbonyl for catalytic purposescz8.j 4 ]might all have served as starting points for early speculation on the reaction mechanism. had such speculation not
been hampered by specific mental blocks (cf. Section 3 . 2 ) .
2.3. The Significance and Status of the 0 x 0 Synthesis
Fig. 13. Dismantling of the Ruhrchemie facilities under the protection ofthe British
Occupation Forcea. the banner reads ”Dismantlers. now begin your work!” [120]
theless, it soon became apparent that regular supply of starting
olefins from the kogasin fraction of FT products or pyrolysis of
F T waxes could not be assured, owing to the uncertain future of
German F T facilities. As a result. a total of only about 3000 t of
C,,--C,, 0x0 product was produced during the period 19531955.
The situation was further complicated by the fact that the
original facility had become technically obsolete, and scientific
information and technical experience gained in the meantime at
the license-free production plants in the United States made it
apparent that an 0x0 process based on the technical specifications of the original Ruhrchemie facility was unlikely to be
successful. Synthetic detergent alcohols at that time were also
not in a position to compete qualitatively with the natural alternatives. Moreover, an excellent supply of short- and mediumchain olefins was available (from cracking plants, or polymer
olefins. C , to C,,), and interest had grown in producing the
corresponding aldehydes resulting from the first step of the 0x0
synthesis (whereas the original 0x0 facility had been designed to
produce higher detergent alcohols in a single step). Perhaps
most important, so much had been learned about the mechanism of the 0 x 0 reaction that promising development potential
was not apparent for the Ruhrchemie technology, based as it
was on batch-slurry operation with a Fischer-Tropsch catalyst
(cf. Section 3.2). Given a loss of interest on the part of Henkel.
BASF (which in the early postwar years. like Ruhrchemie, continued to file patent applications on the 0x0 process through the
Chemische Verwertungsgesellschaft mbH) drew the appropriate
consequences as well, and abandoned its joint partnership with
Ruhrchemie AG[**]in order to pursue its own interests-with
payment of appropriate license fees. As matters developed.
work began in 1958 on the perfection of a second “Ruhrchemie
0x0 process,” culminating in a production capacity of roughly
335000 t/a. The new process attracted the interest of many
licensees. and at its peak constituted the basis for over 2 0 %
of the newly erected 0 x 0 plants throughout the world. This
iln,Fc,n CIwn? Inr. Ed. En,?/ 1994. 33, 2144-2163
The 0x0 synthesis has long been, and remains even now, an
important industrial process; indeed, from a quantitative standpoint among catalytic organometallic processes it i s second only
to the Ziegler process for the manufacture of polyethylene and
polypropylene. World capacity is currently ca. 6 x 10” t:a. Without going into detail on the present state of development with
respect to the major 0x0 producers, we can still predict that
three developments will determine the future significance of the
0x0 synthesis:
As the literature indicates, continuing intense research and
development in the area of hydroformylation is directed toward innovative applications of homogeneous catalysis, including regio- and stereoselective transformations of suitable
starting materials.
0 x 0 facilities in the highly industrialized countries will in the
future be characterized largely by “highly sophisticated” applications involving regioselective hydroformylation. to be
followed in due course by stereoselective reactions leading to
unique and valuable products (i.e.. special intermediates,
formed perhaps enantioselectively). all in conjunction with
tailored catalysts.
World demand for “classical” 0x0 products (plasticizer and
detergent alcohols) will increasingly be met by 0 x 0 facilities in
less developed countries with access to the necessary resources
(raw materials and labor). Many years of free-wheeling licensing politics, coupled with a high degree o f automation
that has reduced the demand for skilled personnel, now
makes it possible for third-world countries (counter to Biblical prophecy) to harvest the fruits of development from fields
they did not themselves sow, contributing “only“ the essential
inexpensive raw materials. Moreover. as the standard of living rises in these countries, so too will demand for certain 0 x 0
products that have increasingly become subjects of concern in
countries with a higher level of “ecological awai-eness” (e.g.,
phthalate plasticizers).
In this respect the 0x0 synthesis will follow a trend already
apparent in chemistry generally : highly industrialized countries
will devote their 0x0 facilities to Roelen reactions and follow-up
steps leading to such highly specialized, “ecologically accept21 51
B. Cornils et al.
able” 0x0 compounds as pharmaceuticals and crop-protection
agents. Consistent with this classical scenario. research and development will prepare the way by perfecting an improved line
of catalysts. The improvements themselves will be fundamental
in nature. encompassing both regioselectivity and stereoselective control over the course of the reaction [Eq. (b)].
3. Lost Opportunities
3.1. Hieber’s Pioneering Work in the Area of Metal
Our current vantage point makes it clear that in the very year
the 0x0 synthesis was discovered the time was ripe for a synergism to develop between the brilliant research efforts of Otto
Roelen and Walter Hieber (1895-1 976). Had this come to pass.
both mechanistic understanding and industrial development of
the hydroformylation reaction would have benefited enormously.
Walter Hieber, born on December 18, 1895. in Waldhausen
(Wiirttemberg) a son of the pastor and later Minister of Education Johannes Hieber. earned his doctorate in 1919 at the University of Tiibingen under the supervision of the coordination
chemist Rudolf F. Weinland. Habilitation followed at the University of Wiirzburg in July 1924. The first theme Hieber addressed in his habilitation thesis blazed the trail for his later
work on the chemistry of carbon monoxide complexes: “It is
not permissible to regard secondary valence simply as a residual
valence or a fragmented main valence.” Following a brief guest
appearance in Jena, Hieber held professorships at the Universities of Heidelberg (until 1932) and Stuttgart before moving in
1935 at the age of 39 to the Technische Hochschule Miinchen as
the successor to Geheimrat (Privy Councilor) Wilhelm Manchot
(1869- 1945). Hieber served in Munich as Professor and Director of the Inorganic Chemical Institute until his retirement in
1964. His predecessor, Manchot, was himself active and quite
successful in the field of metal carbonyls (e.g., [Au(CO)CI].
[Os(CO),CI,]), which was then still in its infancy, and it was for
this reason that the young Hieber’s brilliant work on reactions
of this class of compounds came to Manchot’s attention,[i2S. 1261 Since 1927 Hieber had been trying to establish the
extent to which carbon monoxide in metal complexes could be
replaced by amines as a way of characterizing the metal carbonyls
[M(CO).,] in the form of “elemental complexes.” During the
course of a set of experiments with pentacarbonyliron, suggested
to him by Alwin Mittasch of BASF,[10”125.1271
H’ieber quickly
recognized the principle that came to be known as valence disproportionation.“ *‘I Nonoxidizing acids were used to protonate
the readily accessible carbonylmetalates-anions with the formula [M(CO),J“- containing metal atoms in negative (!) oxidation states -to give a completely new class of “carbonyl hydrides” of the transition metals. The first spectacular example was
21 58
’‘iron carbonyl hydride” with the formula [H,Fe(CO),], a colorless. clear, light- and temperature-sensitive, volatile substance, the
isolation and manipulation of which required the experimental
skills of a master.” 291 Whereas its discoverers immediately assigned the correct structural formula to the compound, including bonding between the metal and atomic hydrogen, other
authors were still ruminating many years later over the isomeric
“hydrocarbonyls,” with structures involving -COH l i g a n d ~ . [ ~ ~ I
In his continuing search for meaningful bonding interpretations Hieber formulated the H,Fe group in [H,Fe(CO),] as a
“pseudonickel atom” (essentially an isoelectronic substitution),
This simple idea led him to the conclusion that a “cobalt carbony1 hydride” with the formula [HCo(CO),] should also be
possible; this compound would effectively complete the series
[Fe(CO),]. [HZFe(CO),], [HCo(CO),I, and [Ni(CO),]. While
still in Heidelberg (1932) he in fact succeeded in demonstrating
the existence of this highly volatile compound by the acid decomposition of amine-containing cobalt carbonyls.“ 301 The
substance proved to be much less stable and even more reactive
than the analogous iron compound. At this point Hieber was
suddenly confronted with competition from America: Coleman
and Blanchard of the Massachusetts Institute o f Technology.
completely unaware of Hieber’s publications (all of which had
been in German). reported in a paper submitted July 28. 1935.
the reaction of K[Co(CO),] with HCI, from which they isolated
“a light yellow crystalline solid which melts at -33 “C to a
sulfur yellow liquid.”[’ 311 Although these authors had clearly
recognized the acidic character of [HCo(CO),], ..the other experiments related to cobalt carbonyl hydride reported by the
cited authors were conducted so inexactly, and the results were
so imprecise, that one can dispense with discussing them further,
especially since they have for some time been largely superseded
by our own investigations.”” 321 Nevertheless, Hieber received
from the American authors “a letter expressly acknowledging our
priority in the discovery of the metal carbonyl hydrides.’”’ 321
Indeed, manuscripts received by journal editors from Hieber in
and on February 9, 1936,[”] clearly do establish this
The synthesis and properties of [HCo(CO),] are described
very precisely in two masterpieces of experimental work carried
out in collaboration with H. Schulten (Fig. 14).L132,
1 3 3 1 Th e
compound was prepared by means of the recently discovered
“base reaction” (now commonly referred to in textbooks as the
“Hieber base reaction”) of the cobalt carbonyl [Co,(CO),] with
barium hydroxide in a high-vacuum apparatus.“
The melting
point was determined “with a pentane thermometer calibrated
by the Imperial Physical-Technical Facility, Berlin” and reported as -26.2 C:[1321
Swabian precision in every detail!
Although Walter Hieber published 200 additional experimental papers on metal carbonyls. those dealing with the carbonyl
hydrides are regarded as the most original. They are also the
most important if one includes in this category the “high-pressure direct syntheses” of metal carbonyls, developed for this
category of substances. Hieber together with H. Schulten and R.
Marin achieved a total synthesis of [HCo(CO),] starting with
cobalt powder and synthesis gas in 1938.“0L.‘“’I Depending on
the pressure and temperature. the major product of the reaction
was either [Co,(CO),] or [HCo(CO),]. This particular piece of
work-fundamentally important with respect to hydroformylaA J I ~ IC‘hriir
E d €nX/. 1994. 33. 1144-2163
Otto Roelen
Obsr Metallcarbonyls. XXV.)
Oarstellung und Elgonachaften
der froion KobaltcarbonylwPueratoffs
Von W. Hissen und H. BCKULTBN
Yit 2 bbbddungrn im Text
Die hisherigen Ergehnisse waren e m kssrke Anregung, nun
suoh den Versueh ear Dnratellung des Kohaltc~rbonylwaaseratolfe
in m i n e r Form zu unternehmen und d i m Verbindung suf ihre
Eigensohnften und ihr Verhslteii zu unterauchen; besanders elaiinwht eraohien nsmentlich der Vorgleich mit dem freien Eisenoarbonylreaaerstoff (CO),FeH,*].
Der hlieruog dee freifm Kohnltanrhonylwwratotla stellten sich
ant6nglioh infolge seiner \enormen Zerseteliohkei t erhebliohe
Sehderigkeiten m den Wag. 8ie gelang schlieQlich durch BLure~enelaung der rllslisoheo Hydridliiaung und aoachliehnde Hoohvskuumdsstillstion. Zur DaraLeUnng der alkaliachen M B U g wurde
reinst- Lristalliaisrtes Kobnltoarbanyl und Bsrytlnuge verwendet.
Die Berytlenge bath den Vortail, do6 dsa bei der Bssenreaktion
entstebende Csrbanat sofort .Is Bariomaarbonst ausgefillt wurde.
Bei der Zersstaung mit Phosphorahre enbtsnd dsher lodiglich
Cerbanylwasserslofl neben gsringw Mengen W-rdsmpf.
Das Gas
wurde dumh 2 s u f -%lo
gekiiblta Sroor'sohe Fallen geleitet, um
den graQtan Teil des Wsssera zuriiokzuhslbo; die Entfernung den
letsten Restea W s l m gelang schlieQlioh aumh unmittelbsre Deatil.
lation liber Phoaphorpsntoxyd. obne daQ eiah hierbei das
Hydrid m t z t e . Der K o h l ~ b o n y l x s s m t a l fkonnte suletet in
einer aof - 190' gekihltan Vorlsge v W g rein kondeniiert werden:
er bildet gut ausgeprS@ hsUgelbe Kristalle, din mit [Ni(Phthrl)JCI.
d x t u n k Bildung dss besehriebenen*) orsngegelben Niedemblsgs
M W .HiWung. rgL dis mohbsnde A W o n g .
1 W.
B.Vmm. 2.-rg.
d g . h m . $19 (IEW. i4G.
Fig. 14. I-acsiinile of the title page of Hieber and Schulten's first paper on [HCoCCO),] [ I 2.1331.
tion as well -was submitted for publication on November 24,
1938.[i0'1very soon after Otto Roelen filed the first 0x0 patent
application.['o1 The relevance of Hieber's pioneering work to
the reaction mechanism of hydroformylation thus becomes obvious. An article in an American journal first alluded to the
possible connection ("We suggest that a hydride is the reagent
effective in the synthesis"[751). and FIAT Report 1000 also
speaks of "hydrocarbonyl Co(CO),(H)," as the reactive species.['" referring to information provided by Otto Roelen of
Ruhrchemie and Kurt Schuster of BASF (cf. Section 3.2).
It remains one of the ironies in the history of science that
Walter Hieber (Fig. 15) never met Otto Roelen, who was almost
exactl! his age. Hieber's students maintained that he never even
sought such a contact. Moreover, the name Roelen is nowhere
cited i n any of Hieber's publications, although he frequently
mentioned the "Reppe chemistry" that was also strongly influ-
Fig 15 Walter Hiebcr during one of his lectures on experimental inorganic chemistry ( o n thc left. hia assistant H. Behi-ens).
enced by his work. By contrast, Otto Roelen kept himself well
informed of results from the laboratory in Munich. and shortly
after the war he proved to be a friendly and interested host in
Oberhausen for field-trip groups from Munich. Helmut
Behrens. at that time a young instructor under hie be^-["^] and
later a professor in Erlangen, recalls: "In the course of a field
trip to Oberhausen in the early 1950s Dr. Roelen asked me to
remain an extra half day so I could discuss with him recent
progress in the Munich metal carbonyl chemistry. His interest
was so keen that he offered to provide me with the company car
to catch up with the rest of the
We have no way of knowing why Hieber never became involved in questions regarding the mechanism of hydroformylation. It is a matter he appears predestined to have tackled. given
his knowledge of the catalytic substance [HCo(CO),]. Was he
marked too strongly by the classical attitude of coordination
chemists like Weinland'? Was his interest in new complexes and
an understanding of the underlying bonding theory more compelling than any effects such materials might have on organic
compounds and any possible industrial applications? Was he
too preoccupied with the metal carbonyl class of compounds per
se? In any event, posterity is keenly aware of this loss o f a unique
opportunity for synergism between academic and industrial
laboratories with mutually complementary expertise. It is also
interesting to speculate whether such a symbiosis might have
significantly hastened the next major advance: thc shift from
organocobalt to organorhodium catalysts for hydroformylation, which in fact began only in the 1 9 7 0 ~ . [ ~ ~ ~
Germany remained the world leader in metal carbonyl chemistry until the end of the 1950s thanks to the tremendous success
of the school surrounding Walter Hieber. As part of one of the
"four-year-plan institutes" designated by the Reich Economics
Ministry, Hieber's research group could depend on the requisite
continuity in its research even during the period 1939--1945.
Given these circumstances, three factors must be taken into
account if one wishes to understand why Roelen's and Hieber's
paths never intersected. First, scientific research was much more
compartmentalized in those days than it is now. Research areas
were "marked out" by specific individuals. and "claims"~ -once
established (usually in the form of concluding sentences in the
relevant groundbreaking papers)-were
generally respected.
Hieber defended his research interests in an especially dedicatcd
way against every potential encroacher, and was thus all the
more annoyed in 1954 when E. 0. Brimm et al. of the Ethyl
Corporation presented a report describing the preparation of
[Mn,(CO),,], the target of a decades-long search." ")I Hieber
himself always respected the territorial claims of others. We are
aware of only a single exception : the isocyanide complexes,
which Friedrich Klages could legitimately have claimed for himself.['401Second, until the groundbreaking discoveries of Ziegler
and Natta, practical applications were essentially ignored by all
organometallic chemists, who restricted their attention to preparative developments and a n understanding of reactivity. I n the
academic world, catalysis was regarded as an erratic field steeped
in empiricism and lacking intellectual pretensions.
Third, mechanistic thinking was not yet well established in
metal complex chemistry in the days of Hieber and Roelen. and
neither scientist was particularly fond of the type of speculative
excursion that would have been required to formulate what we
21 59
B. Cornils et al.
would today regard as the relatively simple set ofsteps constituting the Roelen reaction [olefin - metal complexation, which Roelen already suspected. followed by transformation of the alkyl
group into an acyl group. and subsequent hydride transfer:
Eqs. (c) through (e)]:Is9.
RCH=CH2 + [HCo(COj,]
[RCH, CH2-Co(CO),]
+ CO
+ H2
K C H z C H z CHO
+ [HCo(CO),]
In Fact, it was not until 1960 that these three homogeneousphase reactions were sufficiently well known and understood for
Heck and Breslow to derive the complete mechanism.“ Is] One
might with a bit of restraint surmise that in today’s internationally cross-linked scientific community, potential relationships
between apparently independent research areas would have been
recognized much more quickly. On the other hand. even now.
every innovative field of research requires a certain amount of
time to mature. and we must not forget that in 1938. the year
hydroformylation was discovered, metal carbonyl chemistry
was scarccly a decade old.
3.2. The Long Road to Understanding the 0 x 0 Synthesis
as a Case of Homogeneous Catalysis
It may seem strange that Otto Roelen, a reflective and observant investigator, did not see the nature of the catalysis involved
in hydroformylation for so long-indeed. into the postwar era.
However, given the circumstances of the times and Roelen’s own
particular way of thinking, it all becomes quite understandable.
On one hand. working and living conditions during the Third
Reich were hardly normal. despite an appearance of orderliness
and the regime‘s brutally rigorous attitude toward “law and
order.” Researchers at that time. occupied as they were with a
surplus of militarily vital projects, were a privileged lot. but they
were still restricted in their movements, and subject to the same
limitations and threats as other citizens living in that absolute
war economy. The Ruhrchemie premises experienced a total of
1020 alarms and 27 bombings during the course of the war.r471
and this affected Otto Roelen (who lived in the immediate vicinity of the plant) just as much as it did his contemporaries. A
constant sensation of not having slept enough, together with
persistent thrcats to his very existence, were hardly conducive to
pondering over mechanistic aspects of the 0 x 0 synthesis or questions related to the nature of the catalysis in the new reaction.
Holm et al. expressed the matter directly in similar tones in
FIAT Report 1000:[”1
“This deficiency stems from the wartime necessity of placing
the emphasis upon industrial application and development
rather than on fundamental studies.”
The collective harassment of “comrades” by the Nazi regime
by constant warnings and threats was bound to take
a toll on a loner like Otto Roelen. It prevented him from working properly. and it denied him the leisure necessary for con2160
ducting proper literature searches, as he himself later acknowledged. Symptomatic of the pressures is a Ruhrchemie in-house
newsletter from that period, the content of which ranges from
instructions from the “Head of the Works Committee” to
threats from the “Workforce Combat Patrol Leader.” culminating in “knitting for the final victory”:’90]
“Our participation in the wool collection for the army on the
Eastern Front. Dr. Roelen’s research laboratory is deserving
of special mention. Through his initiatives it was possible to
accomplish the astonishing feat of assembling 167 individual
items for the army, including a large number of lined
vests ... .’’
Moreover. notwithstanding all the apparent efficiency of the
Nazis there was still a shocking level of disorganization in many
employment and research activities,[”] and Roelen‘s involvement i n too many research projects unrelated to the 0x0 synthesis had exceeded his capacity (cf. the report of Otto Roelen’s
interrogation in December 1945 at Wimbledon[Z8.481).
up with the technical literature also became increasingly difficult
under the weight of external factors. In the last years of the war
the literature was hardly accessible at all (several of the German
journals quit publishing altogether after about 1942. including
Clicwiische Bcwkhte. Ckemische Indusirie, and 01 m r l Kolllit),
The way research was organized generally. especially at Ruhrchemie (see above[”’), coupled with the Nazi mania with respect
to secrecy. also prevented the fruitful exchange of ideas with
colleagues. Moreover, in the early phases of his discovery Otto
Roelen had been inclined to undertake personally as much a s
possible of the fundamental work of development and refinement, as well as the preparation and filing of patent applications.
Nevertheless. the most important factor, as Roelen himself later
complained and elaborated in numerous conversations and several lectures on the subject of “Research P s y c h o l ~ g y , ” [9 ~2 1 ~ . ~ ~ .
was a distinct mental block during the war years-probably due
in part to strong preconceptions- against accepting the notion of
a neii, type of catalysis. Like many of his contemporaries, Otto
Roelen was fascinated by catalysis as a spectacular. modern (albeit empirical) science, but he took it for granted that catalysis
generally was equivalent to “chemistry at a catalyst surface”
(Kontakt). in other words that it was a izeierogeneous phenomenon. The idea of homogeneous catalysis was admittedly
not completely unknown (Mittasch and S a b a t i e ~ - [both
~ ~ ] mentioned it briefly), but it was limited conceptually to simpler and
technically unspectacular reactions. and did not yet encompass
the present definition[941of a transformation in which there is
“a molecular distribution of the catalytically active species.
which is therefore highly dispersed and consequently might
be present at very low concentration (into the ppm range).”
Mittasch’s views had an aftereffect as well, such that homogeneous catalysis was viewed exclusively in the context of “a
material ‘invention of nature’.‘’ and the “material ‘substrate’ of
all natural phenomena” (i.e., biocatalysis, according to presentday terminology), This lingering reflection of Berzelius, for
whom “the concept of a catalyst was useful primarily for purposes of physiology,“[9s1was acknowledged as such by Mittasch in his own writings.
Otto Roelcn
For chemists in Otto Roelen’s generation, catalysis in the everyday use of the term referred to heterogrnc~ouslycatalyzed transformations associated with a series of einpirical investigations:
the xnnionia synthesis, coal hydrogenation, hardening of fats.
the Fischcr-Tropsch synthesis, and other industrial-scale and
forward-looking technologies. Organometallic catalysts and reactants w r e essentially unknown except in the case of a few
special and exotic applications (e.g.. the Grignard reaction.
Mond process).
An additional obstacle was the firm assumption that the 0x0
synthesis depended on heterogeneous catalysis. which meant
that any observations to the contrary tended to be dismissed.
Thus. the discovery that the reaction products always contained
significant amounts of cobalt was not taken as evidence suggestive of rhc ~icrii/~cjc,r.ogei~co~~s
nature of the reaction. Ostwald’s
definition of a catalyst a s a “substance that alters the rate of a
reaction without appearing in the final product”IY6’implies that
;I substance that does appear in the final product might be almost
anything. but certainly not a catalyst. In this sense Berzelius’
simpler definition of catalysts as “substances the mere presence
of which confers chemical activity not found in their absence”[‘”] was more useful and less misleading.
Experimental findings should at the least have led Roelen and
his contemporaries to be somewhat suspicious. because the assumption of an unchanged catalyst was incompatible with the
observed facts. which were also not explained by the secondary
hypothesis that the reaction conditions simply resulted in partial
physical dissolution of certain catalyst components. Moreover.
experiments initiated during the war in an attempt to convert
the 0 x 0 synthesis from a reaction based on suspension techniques t o some other alternative were motivated less by a mechanistic way of looking at the reaction than by a desire to increase
the effective utilization of the catalyst. Even developments like
the Leunii variant. the BASF continuous process in a fixed-bed
reactor,”’] and the “diaden” approach (alternate utilization of
the 0x0 and hydrogenation chambers)“ ”I had their origin not
in the possibility that this might be a homogeneously catalyzed
reaction. but rather (as nearly as can be established today) in a
desire to achieve optimal reaction o r temperature control and at
the same time increase productivity (cf. ref. [28]).
This is all in the Face of the fact that Hieber’s most crucial
papers had already been published, and the important observations 01‘ the early 0x0 researchers had already been made. Thus,
even though it seemed self-evident that a commercial (largescale) 0x0 synthesis should be based on the usual catalysts from
the heterogeneous F T process. it very soon became common
practice to compensate for massive losses of cobalt by the introduction of additional soluble cobalt compounds.[28,541 The effect of this material could only have been homogeneous. not
heterogeneous. and it did not in any way take the place of other
components of the FT catalyst; indeed, the additives were deemed
responsible for an observed instability of the FT catalyst itself.
Especially revealing in this context were experiments conducted
by Reppe in Ludwigshafen for a continuous process in a fixedbed reactor. which presupposed subsequent cobalt removal and
separate hydrogenation of the resulting 0x0 aldehydes over copper-chromite catalysts.154.’ 5 On
~ ~ e other curiosity is worth noting: a “miraculous” hydroformylation achieved with metals that
d o not form carbonyl complexes such as calcium, magnesium,
.41ig~’ii ( ‘ l i r r r i . 1111.Ed.
Gi,z/.1994. 3.3. 2144- 2163
and zinc, ingredients that among other things were partially
responsible for the structural composition of the classical FT
catalysts.[”71The person who dreamed up this particular patent
application. an American by the name of Whitman (related to
the famous American poet?) mentions in the general section of
his application in a very pointed and convincing way that the use
of volatile carbonyl complexes actually does nothing but cause
problems, and it might therefore be better to add elements of
atomic number 12-30. which d o not form carbonyl complexes.
At least Otto Roelen’s own patent[’”] was properly cited in this
case: the same could not always be said for other authors.[481
Given the ubiquitous presence of cobalt carbonyls in a11 the
various streams of the 0x0 reaction- reactants, off-gas. and gas
and liquid recycle systems -and in the product itself. Roelen
was led to postulate quite early that volatile “cobalt hydrocarbonyls.” described by Hieber in 1934,[””]were the truly active
0x0 catalysts. This conclusion was influenced by t h e fact that
active 0x0 catalyst could be prepared starting with a wide range
of cobalt compounds.[’*’ as well as by the experimental observation that cobalt,[’”- 1021 but not the oxo-inactive nickel.[”I
formed a hydridocarbonyl (hydride shift
The hydroformylation of ethylene in particular was carried out at 21 very
early date with dissolved cobalt carbonyls. The lack of consistency in Roelen’s ideas regarding the mechanism of the 0x0
synthesis is underscored by the view he expressed its late as 1945
that the threshold temperature for carbonyl formation must lie
below that for formation of cobalt carbide.[’‘] The possibility of
stoichiometric hydroformylation
may also have contributed
to the confusion.
Interestingly, while possible roles for dissolved carbonyls o r
‘“’I in the 0x0 synthesis were
subsequently discussed, Adkins and K r ~ e k ” were
~ ] the first to
describe the reaction explicitly as “nonheterogeneous.” and it
was Storch et a1.,1‘211
Berty and Marko,11061
and Natta[’””who
first explicitly used the descriptive term ”homogeneous.” A
1951 patent application by Kuhlmann. describing the catalytic
application of gas-phase carbonylhydridocobalt.[’081
refers to a
“lack of homogeneity,” but more in the sense of a lack of experimental homogeneity. A parting shot in the battle to formulate
hydroformylation as a heterogeneous process (“. . . an assumption that even now has scattered adherents.. , .” as Falbe[”]
cautiously expressed it in 1967) was fired as late as 1963 by
Aldridge et al.,r1091but vigorously criticized by Macho et al.“ ‘“I
The generation of tetracarbon ylh ydridocobal t. first suspected
by Otto Roeler~[”~and later proposed by numerous authors,[6S.7S.81,10S.I l l . 1 1 2 1 was finally proven by the work of
I. Wender et al.“ 31
Complete unanimity regarding the mechanism of hydroformylation was achieved with the appearance of a persuasive
paper by Heck and Breslow.[1141
Apart from early kinetic investigations by Natta et aI.[”l and their subsequent conclusions
regarding the kinetic order of the reaction,[’” several very divergent interpretations were proposed along the way to an unambiguous formulation of the mechanism, including addition of
[HCo(CO),] to the C-C double bond of the starting olefin followed by a transformation to a more stable hydridocarbonyl
containing less CO (foreshadowing the later dualism of hydridotri- and hydridotetracarbonylcobalt), and a cyclopropyl
(more precisely: cyclopropenone)
with preferen-
tial anti-Markovnikov attack of the formyl group (based on
Reppe and Asinger: a summary is provided in refs. [54.65.115]).
The term "n complex" for the product resulting from the addition of [HCo(CO),] to a double bond wits first suggested by
and then discussed by Roelen in connection with
"crypto ions."["" although until 1947 he had clung to the
possibility of intermediate formation of a carbide in the "genetic
sequence" leading from CO to aldehydes."041 In 1957 Asinger
provided a valuable overview of current ideas on the mechanism
of the 0x0 reaction." I
3.3. Pioneer of lndustrial Homogeneous Catalysis
Although there has been general conseiisiis regarding the nature of the incorporation of "cobalthydi-idocarbonyl" since
1949 and publication of the work of Adkiiis and Krsek (e.g..
refs. [73. 75. 105. 11 11 with mechanisms based on findings by
Martin" 121 and Natta et a1,11(17. 1181). it took many years and
several duels between adherents of ReppeI6'] and Dupont et
a1.l' I 6 l before the currently accepted mechanism of the 0 x 0 reaction was firmly established. This occurred 22 year5 after hydroformylation was discovercd, and then not as a result of efforts
by the discoverer or other protagonists of the 0 x 0 synthesis. but
by Heck and Breslow."
Nevertheless. Otto Roelen can rightfully be identified as the pioneer of modern industrial homogeneous catalysis. His discovery of hydroformylation sensitized
the chemists of his day to the potential for industrial application of organometallic catalysts (ten years prior to the equally
history-making work of Ziegler and Natta). and smoothed the
way for an understanding of the homogeneous version ofcatalysis as an independent, versatile. and commercially successful
method for preparing important basic chemicals and specialty
products. More than that, recognition of the catalytic potential
of metal coordination compounds coupled with further stimulus from the exciting discoveries of ferrocene['3('1 and dibenzenechromiuni" "I-- gave an unprecedented impetus to organometallic chemistry in the 1950s. Carbon monoxide chemistry in
particular cast a bright light on this ascendancy that began with
the groundbreaking work of Otto Roelen and Walter Hieber.
One is compelled to agree with Otto Roelen's later formulation of the quintessence of his personal experience. set against a
background of personal prejudice:["'I
. Fantasy and the powers of imagination can fulfill their
appointed role as intellectual 'sources of raw material' only
if they arc allowed to develop fully and without restriction.
and if nothing stands in the way of one's intellectual processing of it research field in any direction whatsoever. neither
habitual patterns of thought nor preconceptions."
' I . .
In his reflections on his personal failure to recognize the nature of the homogeneous catalysis underlying the oxo reaction,["] Roelen thus paid tribute to the true meaning of his
Favorite author Descartes' "methodological skepticism." He
was indeed the discoverer of the 0x0 synthesis, but not as he
had hoped --the one who unraveled its mechanism. Otto Roelen's special significance. extending into the present, is to be
sought rather in the fact that as the pioneer in the first industrially successful synthesis involving organometallic catalysts he
21 62
B. Cornils et al.
raised the level of consciousness regarding the technical relevance and broad applicability of homogeneous catalysis -in
spite of every attack from aggressive "heterogenophiles.'
Received: March 21. 1994 [A56IE]
German version' A i i ~ q c w .C./IIWI. 1994. / I M . 2210
Translated by Dr. W. E Russey. Huntingdon, PA ( U S A )
[ l ] Lettei- lroin Guthier to Fischcr. June 26, 1922. in: Max-Planck-Instittit Ibr
Kohlenforschung (Archi! MPI). Personnel Record\ (PA) Otto Roelcn (OR)
[2] K W I questionnaire and "proofoi Aryan stitttis" diiled May 4. 1933; Archi\
[ 3 ] Typewritten curriculuin \ittie for O t t o Roelcn from c:i 1941.111. pribate estate
of O R . Kiinigswiiitci-.
[4] Handwritten curriculum vitiic for Otto Roelen dated October 8 , 1924: Ai-chi~
IS] E Pet~old,Luiii .W/iihrigtw Bcsic/iori rlrs H i i i t p i l i i h o r ~ r i o r i i r i ndl,r
~ Hor~sr~li-KiiIi~
ii .4kririi,qi~.vrll,~~./i~if!
111 Dori1iii11111.
Dusseldorf. 1937. p. 18
161 Letter tiom Fischer t o Otto Roelen dated June 78. 1912: Archi\ MPI. PA O R .
(71 i i ) M . Rasch. G i w h i d i i c ilm KWI+ ~ ~ i l i i P / n i - l n i r i i i fiirs
1 9 / 3 1943. VCH. Weinhcim. 1989: b) i n ref. [7;i]. p. 159 ff
181 BASF (no inventor. Schuster [65]later identified Mittasch a n d Schmidt ;is the
lobentors). D R P 293 787. 1913: D R P 395702and 295203. 1914. A. Mitt:i\ch.
M Pier. K . Wiiiklcr ( B A S F ) . D R P 66O619. 1924.
[9] I;. Fischer. H Ti-op\ch. B r ~ w i \ i U
, I~W
I . 4. 276. in particulnr p. 7x4.
[lo] H. Tropsch. 0. Roelen. G i ~ ~ u i i i i i ~ilhli
d i c Kiiiii?i tio11i<>1925. 7. 15.
[I I ] Recommendation from Prof. Bucliercr dated October 7. 1924. Archit! MPI.
PA O R .
[ 121 E\~;iluarioi~ofOtloRoclen'sdissertarion.
Fchruary 21. 1934.Arctuv MPI. PAOK.
[I;] Copy or Otto Roelen's 1914 dissertation in the library of the MPI.
[14] 0. Roclen. DE 497694. 1924'1930.
[ I 51 Deutrches Patentamt. AuAenstclle Berlin. entry in the patcnt register
[I61 H . Tropsch. 0. Roelcn. Brrnri~.\i.Chiw 1924. 5 . 37 G c s o ~ ~ i ~ n .4hh.
dre Kr~ini.
kohl(^ 1925. 7 , 15. 175: 0. Roelen. ihkl. 1925. 7.I 1 1
[I71 0.Roclen. Errliii kohl^, ErrIq115 I ' ~ ~ t ~ i i i / i c w1978.
i/. 524.
[ I X ] F Fischrr. H. Tropsch. ('Iiiw Bo 1926. 59. 836.
1191 Iiifui-rn;ition from the Ai-chi! MPI. PA O R .
[ZO] Letter (1-oin Fischer to the Administrator of the Institute. Mr. Lindeminn.
dated Mai-ch 10. 1931. Archiv MPI No. 01-023.
Archi\! MPI. 99.
[22] 0. Roelcii. Eriliil Knhli, Eri(y!i%P i ~ r r i i i ~ h1977.
~ ~ ~ 30.
i . 456.
[ 3 1 See rcl: [7n]. p 333 If.
H o e c h s ~AG. W r k Ruhroheniie. PA O R .
0. Roelcn (Ruhrchemie A G J . D R P 718509. 1937/1942, D R P 763967. lY36/
1952, 0. Roclen. W. FeiDi (Rulirchemie AG). D R P 764888. 1938
H. Heckel. 0. Roelcn (Ruhrchemie A<;. D R P 764643. 1937/1952.
C oinhined Intelligence 0bJectiLes Sub-Committee (CIOS). Report No.
XXXIII-5. ltcni No. 30: British Intelligence Objectives Sub-Committee
(BIOS). Final Report No 1094. ltcin N o . 30. b I l i ~ 1 m 0i ~i ~ : i k I I?,(,/.
3rd 1'11. 1957. 9. 744 ff.
BIOS. Final Report No. 447. Item No. 30. 1946.
A Hcrriiiann. C. W Kohlpaintner. ;\ii( /IF. C/I(,III. 7v-i.h Loh
Lctter from t h e D r . - F r i t r T o d t Priir. Esren brmch. to Ruhrchemie AG dated
J a n u a r ) 16. 1945. iii Hozchst AG. Werk Ruhrchemie. PA O R .
Correspondence Arcliiv MPI. PA Helmut Pichler
0. Roelcn. C~I~JIII.E j p . D i h k i . 1977. 3. 1 l g .
0 . Ruclen. L ( ~ i I i r ( ~ l bBlol
Ai~riixilFor\di. 1962. 10. 532.
0. Roelcn. tinpublirhed manuscriptb "Eiwe~DarincKost gcgen"
(1'975). "Trinkwiirier in Flaschen" (IY72). '-Zuckervcrzehr iils Krankheitrursache". "Ubci die rogeii?inntC Butter- a n d Margarine-Fragc" (1965). and
"Vei-unreinigiinycii i n R1ieinufcrtilti.atcn" ( 1973)
0 . Roelcn. K I ~ ~ I / . ~\ I~ i ~ ; l ~ . \ ~ i i i ( i ~ i \ 1963
~ r ! ~ (i 5
~ )k / i .
0 . Rocleii. uiipublishcd m:inuscripts -'Uhsi- ;illinentiire Allergcnc" (1974)and
"Getreidekeinic a k Allerpene" (1976).
K . Priibram i n Dii.! Uiii,liikrXro/k,ii CYicniikcr, Oil. / / ( E d . : G Bugge). Verlag
Chemie. Berlin. l929/1930. p. 28Xr.. 207: G. Stein. Tiw S n r c r r w o/ K i i i p . ~ .f%r
C ' a w of Diiiiid Diiiiglris Iloiiiiz iiiid M illi!iiir Croofic.5. Proniethrus. 1993
0 Rocleii. unpublished manuscript\ "Schichtcnhildung im luftclektrischcn
Rauin" (1969). "Wohnungbcnt\tOruiig" l1970). '-Riiumoricntierte p o l w
isicrte Miki-o\rellcn u n d ihrc p h y w l o g i x h c Bedeutung" (1971 1971). a n d
"Pendelkunde" (1980).
0 . Roclen. "Emottk". unpublishcd manuscript (1968).
c'. P Siio\v, Dir :wi'i Kiiliiirwi. Klett. Stuttgnrt. 1959, I71r nio C ' ~ i l i i ~ r , irird
7 l i c & imii/i<~
R i ~w /i i ti o i iCambridge
University Presa. Cambridge. England.
H . Krcuzei-. W, Klein. L'lwi Siroii.\ " D ~:iwi
P Kiilriiriw C. P. Sirobi 5 Tlii,.\i, iii
rl1,r Dixkii,s\i(i~i
". Klett-Cottii ini Dcutschen T~ischenbuch-Vcrlag.Miinchen.
1421 K . Steinbuch. kiiiw 11~ ~ r t i , ~ ~ ~ i i i i i iDcutsche
Vcrlags-Anstalt. Stuttgart. 1968.
Otto Roelen
(431 K Rcuiii:inn. "Frankfurter Allgemeine Zeitung". August 15. 1987.
[44] E.WOK. "Die Zeit". March 13. 1964
I451 0. Roelcn. honorary doctorate acceptance address a t the Technische Hochschule. Anchcn. January 21. 1983.
[4h] G , Plumpe. Dir I G.~ i i r b o i i i i r / i i . \ r r i [A<;.
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[47] M . R:i\ch. G c > \ i 4 i < h r i , rier R n h r c h r i i i i e AG, Privatdruck. unpublished
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[JX] BIOS. Fiiial Report No. 511. Item No. 30.
[49]C . D Frohiiiiip, B. Coi-nils. F[idrmurhoii 1974 ( I I ) . 143; B.
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1933. 14. 3.
[53] D. F Smith. C . 0. H a n k . P. L. Golden. J. A i n . Chcwt. Soc. 1930. 52, 3221.
1541 BIOS mil rield Information Agencl. Technical (FIAT). FIAT Final Report
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[55] B. C'oi-niI\. W. Rottig in ( ' / i o i i i c r ( i / i . s r o / l e ini.\ Koh/iJ (Ed.: J. Falbe). Thieme,
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h] W Rotti:. F Duftschiiiid. l : / h t i i n i i i . ~€iiri./,/. Rdi. Chwt.,3rdcrl. 1957. 9, 742.
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[hO] Minute\ 01' the Ruhrchemie Aktiengesellschaft Executive Board meeting of
Fehi ti.iry 6. 1940. VS-Akten Hoechst AG. Wcrk Ruhrchemie (Ablage
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1631 Nnt.iri/ed document No. 220'1940. Dr. Karl Lohmar. notary. Oberhausen
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[h4] A. WilIciii;irt. Bid/. Sol.. C h i i i i . Fr. 1947. /4(5).
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[hh] .AiiaIcip~~u~
III I-ct: [Q]. meeting 01' November 13. 1940
[h7] An;ilogous to I-cf.[61].meeting of November 19, 1941.
[hX] Lettci- Il.niii the Owgesellschalt mhH to Ruhrchemie AG dated February 2X.
1941 (Ablage Rcchtsabteilung. Hoechst AG. Werk Ruhrchemie)
1691 Article\ of ,is(;ociatioii for the Chemische Vernertiingsgesellsch'ift OberIi.i~i\cii GinbH. entered i n t o by the Ruhrchemie AG and the I . G. Farbenindu\ti-ic AG o n Dcceinber 1 1 . 1940 (Ahlage Rechtsabteilung. Hoechst AG,
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1701 Aiiit\pci-icht Oherhausen-Rhld.. Handelsi-egister Abteilung B. No. 83 from
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1711 ('10s. Report No XXVII-18. Item No. 23, 1945.
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[75] H. Adkins. G. tirsrk, J. A i i t . C/t~wi.
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