Walter Julius Reppe (29 July 1892 in
Göringen – 26 July 1969 in
Heidelberg
Heidelberg (; ; ) is the List of cities in Baden-Württemberg by population, fifth-largest city in the States of Germany, German state of Baden-Württemberg, and with a population of about 163,000, of which roughly a quarter consists of studen ...
) was a German
chemist
A chemist (from Greek ''chēm(ía)'' alchemy; replacing ''chymist'' from Medieval Latin ''alchemist'') is a graduated scientist trained in the study of chemistry, or an officially enrolled student in the field. Chemists study the composition of ...
. He is notable for his contributions to the chemistry of
acetylene
Acetylene (Chemical nomenclature, systematic name: ethyne) is a chemical compound with the formula and structure . It is a hydrocarbon and the simplest alkyne. This colorless gas is widely used as a fuel and a chemical building block. It is u ...
.
Education and career
Walter Reppe began his study of the natural sciences
University of Jena
The University of Jena, officially the Friedrich Schiller University Jena (, abbreviated FSU, shortened form ''Uni Jena''), is a public research university located in Jena, Thuringia, Germany.
The university was established in 1558 and is cou ...
in 1911. Interrupted by the
First World War
World War I or the First World War (28 July 1914 – 11 November 1918), also known as the Great War, was a World war, global conflict between two coalitions: the Allies of World War I, Allies (or Entente) and the Central Powers. Fighting to ...
, he obtained his
doctorate
A doctorate (from Latin ''doctor'', meaning "teacher") or doctoral degree is a postgraduate academic degree awarded by universities and some other educational institutions, derived from the ancient formalism '' licentia docendi'' ("licence to teach ...
in
Munich
Munich is the capital and most populous city of Bavaria, Germany. As of 30 November 2024, its population was 1,604,384, making it the third-largest city in Germany after Berlin and Hamburg. Munich is the largest city in Germany that is no ...
in 1920.
In 1921, Reppe worked for
BASF
BASF SE (), an initialism of its original name , is a European Multinational corporation, multinational company and the List of largest chemical producers, largest chemical producer in the world. Its headquarters are located in Ludwigshafen, Ge ...
's main laboratory. From 1923, he worked on the
catalytic
Catalysis () is the increase in reaction rate, rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst ...
dehydration of
formamide
Formamide is an amide derived from formic acid. It is a colorless liquid which is miscible with water and has an ammonia-like odor. It is chemical feedstock for the manufacture of sulfa drugs and other pharmaceuticals, herbicides and pesticides, ...
to
prussic acid
Hydrogen cyanide (formerly known as prussic acid) is a chemical compound with the formula HCN and structural formula . It is a highly toxic and flammable liquid that boils slightly above room temperature, at . HCN is produced on an industrial s ...
in the
indigo
InterGlobe Aviation Limited (d/b/a IndiGo), is an India, Indian airline headquartered in Gurgaon, Haryana, India. It is the largest List of airlines of India, airline in India by passengers carried and fleet size, with a 64.1% domestic market ...
laboratory, developing this procedure for industrial use. In 1924, he left research for 10 years, only resuming it in 1934.
Acetylene chemistry
Reppe began his interest in
acetylene
Acetylene (Chemical nomenclature, systematic name: ethyne) is a chemical compound with the formula and structure . It is a hydrocarbon and the simplest alkyne. This colorless gas is widely used as a fuel and a chemical building block. It is u ...
in 1928. Acetylene is a gas which can take part in many
chemical reaction
A chemical reaction is a process that leads to the chemistry, chemical transformation of one set of chemical substances to another. When chemical reactions occur, the atoms are rearranged and the reaction is accompanied by an Gibbs free energy, ...
s. However, it is explosive and accidents often occurred. Because of this danger, small quantities of acetylene were used at a time, and always without high pressures. In fact, it was forbidden to compress acetylene over 1.5 bar at BASF.
To work with acetylene safely, Reppe designed special test tubes, the so-called "Reppe glasses" — stainless steel spheres with screw-type cap, which permitted high pressure experiments. The efforts ended finally with a large number of interrelated reactions, known as ''Reppe chemistry''.
"Reppe Chemie"
The high pressure reactions catalysed by heavy metal
acetylide
In chemistry, an acetylide is a compound that can be viewed as the result of replacing one or both hydrogen atoms of acetylene (ethyne) by metallic or other cations. Calcium carbide is an important industrial compound, which has long been used ...
s, especially
copper acetylide, or metal
carbonyl
In organic chemistry, a carbonyl group is a functional group with the formula , composed of a carbon atom double bond, double-bonded to an oxygen atom, and it is divalent at the C atom. It is common to several classes of organic compounds (such a ...
s are called Reppe chemistry. Reactions can be classified into four large classes:
* The
vinyl
Vinyl may refer to:
Chemistry
* Polyvinyl chloride (PVC), a particular vinyl polymer
* Vinyl cation, a type of carbocation
* Vinyl group, a broad class of organic molecules in chemistry
* Vinyl polymer, a group of polymers derived from vinyl ...
ization according to the equation:
:
* Catalytic
ethynylation of
aldehyde
In organic chemistry, an aldehyde () (lat. ''al''cohol ''dehyd''rogenatum, dehydrogenated alcohol) is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred ...
s (although the milder
Favorskii reaction
The Favorskii reaction is an organic chemistry reaction between an alkyne and a carbonyl group, under basic conditions. The reaction was discovered in the early 1900s by the Russian chemist Alexei Yevgrafovich Favorskii.
When the carbonyl is a ...
was reported earlier):
:
* Reactions with
carbon monoxide
Carbon monoxide (chemical formula CO) is a poisonous, flammable gas that is colorless, odorless, tasteless, and slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the si ...
:
:
:
This simple synthesis was used to prepare
acrylic acid
Acrylic acid (IUPAC: prop-2-enoic acid) is an organic compound with the formula CH2=CHCOOH. It is the simplest unsaturated carboxylic acid, consisting of a vinyl group connected directly to a carboxylic acid terminus. This colorless liquid has ...
derivatives for the production of
acrylic glass
Poly(methyl methacrylate) (PMMA) is a synthetic polymer derived from methyl methacrylate. It is a transparent thermoplastic, used as an engineering plastic. PMMA is also known as acrylic, acrylic glass, as well as by the trade names and bran ...
.
* The cyclic
polymerization
In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many fo ...
or
cyclo-oligomerization of acetylene to
cyclooctatetraene
1,3,5,7-Cyclooctatetraene (COT) is an unsaturated derivative of cyclooctane, with the formula C8H8. It is also known as nnulene. This polyunsaturated hydrocarbon is a colorless to light yellow flammable liquid at room temperature. Because of ...
, which is one of the most important applications of
template reactions. The reaction occurs at a
nickel
Nickel is a chemical element; it has symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive, but large pieces are slo ...
(II) centre, where it is supposed that four acetylene molecules occupy four sites around the metal, and react simultaneously to give the product.
:
If a competing ligand such as
triphenylphosphine is present in sufficient proportion to occupy one coordination site, then room is left for only three acetylene molecules, and these come together to form
benzene
Benzene is an Organic compound, organic chemical compound with the Chemical formula#Molecular formula, molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar hexagonal Ring (chemistry), ring with one hyd ...
:
This reaction provided an unusual route to
benzene
Benzene is an Organic compound, organic chemical compound with the Chemical formula#Molecular formula, molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar hexagonal Ring (chemistry), ring with one hyd ...
and especially to
cyclooctatetraene
1,3,5,7-Cyclooctatetraene (COT) is an unsaturated derivative of cyclooctane, with the formula C8H8. It is also known as nnulene. This polyunsaturated hydrocarbon is a colorless to light yellow flammable liquid at room temperature. Because of ...
, which was difficult to prepare otherwise.
Products from these four reaction types proved to be versatile intermediates in the syntheses of lacquers, adhesives, foam materials, textile fibers, and pharmaceuticals could now be produced.
Post-war
After the
Second World War
World War II or the Second World War (1 September 1939 – 2 September 1945) was a World war, global conflict between two coalitions: the Allies of World War II, Allies and the Axis powers. World War II by country, Nearly all of the wo ...
, Reppe led the research of BASF from 1949 up to his retirement in 1957. From 1952 to 1966, he also sat on the supervisory board. He was also a professor at the
University of Mainz
The Johannes Gutenberg University Mainz () is a public research university in Mainz, Rhineland Palatinate, Germany. It has been named after the printer Johannes Gutenberg since 1946. it had approximately 32,000 students enrolled in around 100 a ...
and TH
Darmstadt
Darmstadt () is a city in the States of Germany, state of Hesse in Germany, located in the southern part of the Frankfurt Rhine Main Area, Rhine-Main-Area (Frankfurt Metropolitan Region). Darmstadt has around 160,000 inhabitants, making it the ...
from 1951 and 1952 respectively. Together with
Otto Bayer and
Karl Ziegler he received the
Werner von Siemens Ring in 1960 for expanding the scientific knowledge on and for the technical development of new synthetic high-molecular materials.
Legacy
Most of the industrial processes that were developed by Reppe and coworkers have been superseded, largely because the chemical industry has shifted from coal as feedstock to oil. Alkenes from thermal cracking are readily available, but acetylene is not.
Together with his contemporaries
Otto Roelen
Otto Roelen (22 March 1897 – 30 January 1993) was a German chemist who pioneered using carbon monoxide to synthesize of organic compounds.
Roelen was born in Mülheim, Germany and studied chemistry and graduated in 1922 from Technische Hochschu ...
,
Karl Ziegler,
Hans Tropsch, and
Franz Fischer, Reppe was a leader in demonstrating the utility of metal-catalyzed reactions in large scale synthesis of organic compounds. The economic benefits demonstrated by this research motivated the eventual flowering of
organometallic chemistry
Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and so ...
and its close connection to industry.
Further reading
* ''Neue Entwicklungen auf dem Gebiet der Chemie des Acetylen und Kohlenoxyds'' (New developments in the area of the chemistry acetylene and carbon monoxide). Springer Berlin, Göttingen, Heidelberg. 1949. 184 pages.
*
References
{{DEFAULTSORT:Reppe, Walter
20th-century German chemists
University of Jena alumni
Ludwig Maximilian University of Munich alumni
Academic staff of Johannes Gutenberg University Mainz
Werner von Siemens Ring laureates
Members of the Royal Swedish Academy of Sciences
1892 births
1969 deaths
Knights Commander of the Order of Merit of the Federal Republic of Germany
German organic chemists
People from Eisenach