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Rainer Ludwig Claisen (; 14 January 1851 – 5 January 1930) was a German
chemist A chemist (from Greek ''chēm(ía)'' alchemy; replacing ''chymist'' from Medieval Latin ''alchemist'') is a scientist trained in the study of chemistry. Chemists study the composition of matter and its properties. Chemists carefully describe th ...
best known for his work with condensations of
carbonyl In organic chemistry, a carbonyl group is a functional group composed of a carbon atom double-bonded to an oxygen atom: C=O. It is common to several classes of organic compounds, as part of many larger functional groups. A compound containing a ...
s and
sigmatropic rearrangement A sigmatropic reaction in organic chemistry is a pericyclic reaction wherein the net result is one σ-bond is changed to another σ-bond in an uncatalyzed intramolecular reaction. The name ''sigmatropic'' is the result of a compounding of the long ...
s. He was born in
Cologne Cologne ( ; german: Köln ; ksh, Kölle ) is the largest city of the German western States of Germany, state of North Rhine-Westphalia (NRW) and the List of cities in Germany by population, fourth-most populous city of Germany with 1.1 m ...
as the son of a
jurist A jurist is a person with expert knowledge of law; someone who analyses and comments on law. This person is usually a specialist legal scholar, mostly (but not always) with a formal qualification in law and often a legal practitioner. In the Uni ...
and studied chemistry at the university of
Bonn The federal city of Bonn ( lat, Bonna) is a city on the banks of the Rhine in the German state of North Rhine-Westphalia, with a population of over 300,000. About south-southeast of Cologne, Bonn is in the southernmost part of the Rhine-Ruhr r ...
(1869), where he became a member of
K.St.V. Arminia The Katholischer Studentenverein Arminia (Catholic Students Society Arminia), also know as K.St.V. Aminia) is one of Germany's oldest Catholic male student societies. History Arminia is a student association founded on 6 November 1863 at the ...
. He served in the
army An army (from Old French ''armee'', itself derived from the Latin verb ''armāre'', meaning "to arm", and related to the Latin noun ''arma'', meaning "arms" or "weapons"), ground force or land force is a fighting force that fights primarily on ...
as a nurse in 1870–1871 and continued his studies at
Göttingen University Göttingen (, , ; nds, Chöttingen) is a university city in Lower Saxony, central Germany, the capital of the eponymous district. The River Leine runs through it. At the end of 2019, the population was 118,911. General information The orig ...
. He returned to the
University of Bonn The Rhenish Friedrich Wilhelm University of Bonn (german: Rheinische Friedrich-Wilhelms-Universität Bonn) is a public research university located in Bonn, North Rhine-Westphalia, Germany. It was founded in its present form as the ( en, Rhine U ...
in 1872 and started his
academic An academy (Attic Greek: Ἀκαδήμεια; Koine Greek Ἀκαδημία) is an institution of secondary education, secondary or tertiary education, tertiary higher education, higher learning (and generally also research or honorary membershi ...
career at the same university in 1874. He died in 1930 in Godesberg am Rhein (near
Bonn The federal city of Bonn ( lat, Bonna) is a city on the banks of the Rhine in the German state of North Rhine-Westphalia, with a population of over 300,000. About south-southeast of Cologne, Bonn is in the southernmost part of the Rhine-Ruhr r ...
).


Career


Scientific contributions

* Described the
condensation Condensation is the change of the state of matter from the gas phase into the liquid phase, and is the reverse of vaporization. The word most often refers to the water cycle. It can also be defined as the change in the state of water vapor to ...
of
aromatic In chemistry, aromaticity is a chemical property of cyclic ( ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to satur ...
aldehyde In organic chemistry, an aldehyde () is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred to as an aldehyde but can also be classified as a formyl grou ...
s with
aliphatic In organic chemistry, hydrocarbons ( compounds composed solely of carbon and hydrogen) are divided into two classes: aromatic compounds and aliphatic compounds (; G. ''aleiphar'', fat, oil). Aliphatic compounds can be saturated, like hexane, or ...
aldehydes or
ketone In organic chemistry, a ketone is a functional group with the structure R–C(=O)–R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group –C(=O)– (which contains a carbon-oxygen double bo ...
s in 1881. This variation of the now well-known
aldol condensation An aldol condensation is a condensation reaction in organic chemistry in which two carbonyl moieties (of aldehydes or ketones) react to form a β-hydroxyaldehyde or β-hydroxyketone (an aldol reaction), and this is then followed by dehydration to ...
reaction is called the Claisen–Schmidt condensation. * Discovered (1887) the condensation reaction of an
ester In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ar ...
with an activated
methylene group In organic chemistry, a methylene group is any part of a molecule that consists of two hydrogen atoms bound to a carbon atom, which is connected to the remainder of the molecule by two single bonds. The group may be represented as , where the '< ...
, now known as the
Claisen condensation The Claisen condensation is a carbon–carbon bond forming reaction that occurs between two esters or one ester and another carbonyl compound in the presence of a strong base, resulting in a β-keto ester or a β-diketone. It is named after Raine ...
. * Synthesis of
cinnamate Cinnamic acid is an organic compound with the formula C6H5-CH=CH- COOH. It is a white crystalline compound that is slightly soluble in water, and freely soluble in many organic solvents. Classified as an unsaturated carboxylic acid, it occurs na ...
s by reacting aromatic aldehydes with esters. The reaction is known as the Claisen reaction and was described by Claisen for the first time in 1890. * Discovered the thermally induced rearrangement of
allyl In organic chemistry, an allyl group is a substituent with the structural formula , where R is the rest of the molecule. It consists of a methylene bridge () attached to a vinyl group (). The name is derived from the scientific name for garlic, ...
phenyl In organic chemistry, the phenyl group, or phenyl ring, is a cyclic group of atoms with the formula C6 H5, and is often represented by the symbol Ph. Phenyl group is closely related to benzene and can be viewed as a benzene ring, minus a hydrogen ...
ether In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again be c ...
in 1912. He details its reaction mechanism in his last scientific publication (1925). In his honor, the reaction has been named the
Claisen rearrangement The Claisen rearrangement is a powerful carbon–carbon bond-forming chemical reaction discovered by Rainer Ludwig Claisen. The heating of an allyl vinyl ether will initiate a ,3sigmatropic rearrangement to give a γ,δ-unsaturated carbonyl, d ...
. * Synthesis of
isatin Isatin, also known as tribulin, is an organic compound derived from indole with formula C8H5NO2. The compound was first obtained by Otto Linné Erdman and Auguste Laurent in 1840 as a product from the oxidation of indigo dye by nitric acid and ...
via a process known as the
Claisen isatin synthesis Claisen may refer to: *Rainer Ludwig Claisen, a German chemist **Claisen rearrangement, a reaction of a allyl vinyl ether to a γ,δ-unsaturated carbonyl **Claisen condensation, a reaction between esters and carbonyl compounds in the presence of ...
, described for the first time in 1879. * Designer of a special distillation flask, now known as the Claisen flask.A description and depiction of Claisen's flask appeared in: Translation of footnote (31) o
pages 177–178
which describes and depicts Claisen's flask: 31) During vacuum distillations that were often performed during this and other work, I used advantageously fractionation flasks of a form like those seen in the figures below. The neck of the flask is, as in the case of the distillation apparatus that was devised by Kahlbaum, in two parts; one piece serves for the installation of the capillary tube, ndthe attachment on the side, for the insertion of the thermometer; the upper openings are of such width that a piece of rubber tubing can conveniently be put on
hem A hem in sewing is a garment finishing method, where the edge of a piece of cloth is folded and sewn to prevent unravelling of the fabric and to adjust the length of the piece in garments, such as at the end of the sleeve or the bottom of the ga ...
and on the other side, the capillary tube and the thermometer can still be easily inserted. One thus avoided the troubles that the use of two-holed rubber stoppers bring with them — the frequent breaking off of the capillary threads and the crushing of the thermometer. Furthermore, these fractionation flasks have still other advantages, which caused me to prefer them to the apparatus by which Anschütz avoided, in a clever way, the two-hole stopper. A surge of the liquid up into the condenser during fitful boiling is less possible here than in the case of a simple one-necked flask; it can be completely avoided if one pours into the (in this case not constricted) side tube (Figure II) a few coarse pieces of glass, which break the thrust of the upwards rushing liquid. One can fill — completely or partially — the space above the glass pieces with glass beads (naturally only in the case of liquids of not too high boiling point), and thus combine the advantages of Hempel's column with vacuum distillation. In the latter way, I have been able to achieve many faster separations and many sharper boiling points than by the usual procedure. However, even without the glass pieces and beads, the differences, highlighted by Anschütz, of heating over an open flame and of distillation using an oil bath don't assert themselves, in large measure, as hey doin the case of the simple one-necked flask. Flasks of the type mentioned are custom made by the glass blowing firm of C. Heinz & Co. in Aachen. (For literature on this subject, see: Kahlbaum, ''Boiling Temperature and Pressure'', Leipzig, 1885; Anschütz, ''Distillation Under Reduced Pressure'', Bonn 1887; Hantzsch, these ''Annals'' 249: 57.) The use of a short Hempel's column during vacuum distillation has also been recommended by Michael (''Journal für praktische Chemie'', 47: 197).
With the increased modularity of modern glassware this functionality is now often achieved with a Claisen adapter, of which there are many types, attached to a normal flask.


See also

*
Cinnamic acid Cinnamic acid is an organic compound with the formula C6H5-CH=CH- COOH. It is a white crystalline compound that is slightly soluble in water, and freely soluble in many organic solvents. Classified as an unsaturated carboxylic acid, it occurs n ...
*
Dibenzylideneacetone Dibenzylideneacetone or dibenzalacetone, often abbreviated dba, is an organic compound with the formula C17H14O. It is a pale-yellow solid insoluble in water, but soluble in ethanol. It was first prepared in 1881 by the German chemist Rainer Ludwi ...
*
Tetrahedral carbonyl addition compound A tetrahedral intermediate is a reaction intermediate in which the bond arrangement around an initially double-bonded carbon atom has been transformed from trigonal to tetrahedral. Tetrahedral intermediates result from nucleophilic addition to a c ...


References

*W Pötsch. ''Lexikon bedeutender Chemiker'' (VEB Bibliographisches Institut Leipzig, 1989) ()


Notes

{{DEFAULTSORT:Claisen, Rainer Ludwig 1851 births 1930 deaths Organic chemists 20th-century German chemists University of Bonn alumni University of Bonn faculty 19th-century German chemists