Wilhelm Rudolph Fittig (6 December 183519 November 1910) 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 ...
. He discovered the
pinacol coupling reaction A pinacol coupling reaction is an organic reaction in which a carbon–carbon bond is formed between the carbonyl groups of an aldehyde or a ketone in presence of an electron donor in a free radical process. The reaction product is a vicinal diol. ...
,
mesitylene
Mesitylene or 1,3,5-trimethylbenzene is a derivative of benzene with three methyl substituents positioned symmetrically around the ring. The other two isomeric trimethylbenzenes are 1,2,4-trimethylbenzene (pseudocumene) and 1,2,3-trimethylbenze ...
,
diacetyl
Diacetyl (IUPAC systematic name: butanedione or butane-2,3-dione) is an organic compound with the chemical formula (CH3CO)2. It is a yellow liquid with an intensely buttery flavor. It is a vicinal diketone (two C=O groups, side-by-side). Diacet ...
and
biphenyl
Biphenyl (also known as diphenyl, phenylbenzene, 1,1′-biphenyl, lemonene or BP) is an organic compound that forms colorless crystals. Particularly in older literature, compounds containing the functional group consisting of biphenyl less one ...
. Fittig studied the action of
sodium
Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable iso ...
on
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 and
hydrocarbon
In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ex ...
s. He discovered the
Fittig reaction
Wilhelm Rudolph Fittig (6 December 183519 November 1910) was a German chemist. He discovered the pinacol coupling reaction, mesitylene, diacetyl and biphenyl. Fittig studied the action of sodium on ketones and hydrocarbons. He discovered the Fit ...
or
Wurtz–Fittig reaction for the synthesis of alkylbenzenes, he proposed a diketone structure for
benzoquinone Benzoquinone (C6H4O2) is a quinone with a single benzene ring. There are 2 (out of 3 hypothetical) benzoquinones:
* 1,4-Benzoquinone, most commonly, right image (also ''para''-benzoquinone, ''p''-benzoquinone, ''para''-quinone, or just quinone)
* 1 ...
and isolated
phenanthrene
Phenanthrene is a polycyclic aromatic hydrocarbon (PAH) with formula C14H10, consisting of three fused benzene rings. It is a colorless, crystal-like solid, but can also appear yellow. Phenanthrene is used to make dyes, plastics and pesticides, e ...
from
coal tar
Coal tar is a thick dark liquid which is a by-product of the production of coke and coal gas from coal. It is a type of creosote. It has both medical and industrial uses. Medicinally it is a topical medication applied to skin to treat psoriasi ...
. He discovered and synthesized the first
lactone
Lactones are cyclic carboxylic esters, containing a 1-oxacycloalkan-2-one structure (), or analogues having unsaturation or heteroatoms replacing one or more carbon atoms of the ring.
Lactones are formed by intramolecular esterification of the co ...
s and investigated structures of
piperine
Piperine, along with its isomer chavicine, is the alkaloid responsible for the pungency of black pepper and long pepper. It has been used in some forms of traditional medicine.
Preparation
Due to its poor solubility in water, piperine is typica ...
naphthalene
Naphthalene is an organic compound with formula . It is the simplest polycyclic aromatic hydrocarbon, and is a white crystalline solid with a characteristic odor that is detectable at concentrations as low as 0.08 ppm by mass. As an aromati ...
and
fluorene
Fluorene , or 9''H''-fluorene is an organic compound with the formula (C6H4)2CH2. It forms white crystals that exhibit a characteristic, aromatic odor similar to that of naphthalene. It has a violet fluorescence, hence its name. For commercial pu ...
.
Career
Fittig studied chemistry at the
University of Göttingen
The University of Göttingen, officially the Georg August University of Göttingen, (german: Georg-August-Universität Göttingen, known informally as Georgia Augusta) is a public research university in the city of Göttingen, Germany. Founded ...
, graduating as
Ph.D.
A Doctor of Philosophy (PhD, Ph.D., or DPhil; Latin: or ') is the most common degree at the highest academic level awarded following a course of study. PhDs are awarded for programs across the whole breadth of academic fields. Because it is a ...
with a dissertation on
acetone
Acetone (2-propanone or dimethyl ketone), is an organic compound with the formula . It is the simplest and smallest ketone (). It is a colorless, highly volatile and flammable liquid with a characteristic pungent odour.
Acetone is miscib ...
in 1858, under the supervision of
Heinrich Limpricht
Heinrich Limpricht (21 April 1827 – 13 May 1909) was a German chemist. Limpricht was a pupil of Friedrich Wöhler; he worked on the chemistry of furans and pyrroles, discovering furan in 1870.
In 1852 he became lecturer and in 1855 extraor ...
and
Friedrich Wöhler
Friedrich Wöhler () FRS(For) HonFRSE (31 July 180023 September 1882) was a German chemist known for his work in inorganic chemistry, being the first to isolate the chemical elements beryllium and yttrium in pure metallic form. He was the firs ...
. He subsequently held several appointments at Göttingen, becoming Wöhler's assistant in 1858,
privatdozent
''Privatdozent'' (for men) or ''Privatdozentin'' (for women), abbreviated PD, P.D. or Priv.-Doz., is an academic title conferred at some European universities, especially in German-speaking countries, to someone who holds certain formal qualific ...
in 1860 and extraordinary professor in 1870. In 1870 he was appointed full professor at
University of Tübingen
The University of Tübingen, officially the Eberhard Karl University of Tübingen (german: Eberhard Karls Universität Tübingen; la, Universitas Eberhardina Carolina), is a public research university located in the city of Tübingen, Baden-Wü ...
and in 1876 at
Strassburg
Strasbourg (, , ; german: Straßburg ; gsw, label=Bas Rhin Alsatian, Strossburi , gsw, label=Haut Rhin Alsatian, Strossburig ) is the prefecture and largest city of the Grand Est region of eastern France and the official seat of the Eur ...
, where the laboratories were erected from his designs.
Fittig's research covered wide areas of organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; ...
. The 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 and 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 provided material for his earlier work. He observed that aldehydes and ketones may suffer reduction in neutral
Neutral or neutrality may refer to:
Mathematics and natural science Biology
* Neutral organisms, in ecology, those that obey the unified neutral theory of biodiversity
Chemistry and physics
* Neutralization (chemistry), a chemical reaction in ...
, alkaline
In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a base (chemistry), basic, ionic compound, ionic salt (chemistry), salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as ...
, and sometimes acid solution to secondary and tertiary glycol
A diol is a chemical compound containing two hydroxyl groups ( groups). An Aliphatic compound, aliphatic diol is also called a glycol. This pairing of functional groups is pervasive, and many subcategories have been identified.
The most common ...
s, substances which he named pinacones; and also that certain pinacones when distilled with dilute sulfuric acid
Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...
gave compounds, which he named pinacolines. The unsaturated acids also received much attention, and he discovered the internal anhydride
An organic acid anhydride is an acid anhydride that is an organic compound. An acid anhydride is a compound that has two acyl groups bonded to the same oxygen atom. A common type of organic acid anhydride is a carboxylic anhydride, where the pa ...
s of oxyacid
An oxyacid, oxoacid, or ternary acid is an acid that contains oxygen. Specifically, it is a compound that contains hydrogen, oxygen, and at least one other element, with at least one hydrogen atom bonded to oxygen that can dissociate to produce ...
s, termed lactone
Lactones are cyclic carboxylic esters, containing a 1-oxacycloalkan-2-one structure (), or analogues having unsaturation or heteroatoms replacing one or more carbon atoms of the ring.
Lactones are formed by intramolecular esterification of the co ...
s. He also discovered what is now known as the pinacol rearrangement
The pinacol–pinacolone rearrangement is a method for converting a 1,2-diol to a carbonyl compound in organic chemistry. The 1,2-rearrangement takes place under acidic conditions. The name of the rearrangement reaction comes from the rearrangemen ...
, whereby 1,2-diols rearrange to aldehydes or ketones under acid catalysis
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
. His work involved the preparation of 2,3-dimethyl-2,3-butanediol (pinacol
Pinacol is a white solid organic compound. It is a diol that has hydroxyl groups (-OH) on vicinal carbon atoms.
Preparation
It may be produced by the pinacol coupling reaction from
acetone:
Reactions
As a vicinal-diol, it can rearrange t ...
) from acetone
Acetone (2-propanone or dimethyl ketone), is an organic compound with the formula . It is the simplest and smallest ketone (). It is a colorless, highly volatile and flammable liquid with a characteristic pungent odour.
Acetone is miscib ...
, followed by the rearrangement to 3,3-dimethylbutanone (pinacolone
Pinacolone (3,3-dimethyl-2-butanone) is an important ketone in organic chemistry. It is a colorless liquid and has a slight peppermint- or camphor- odor. It is a precursor to triazolylpinacolone in the synthesis of the fungicide triadimefon and i ...
), which was then oxidised with dichromate to trimethylacetic acid
Pivalic acid is a carboxylic acid with a molecular formula of (CH3)3CCO2H. This colourless, odiferous organic compound is solid at room temperature. A common abbreviation for the pivalyl or pivaloyl group (''t''-BuC(O)) is Piv and for pivalic acid ...
. Fittig's interpretation of his results was incorrect and the products formed were not identified until more than a decade later when Aleksandr Butlerov
Alexander Mikhaylovich Butlerov (Алекса́ндр Миха́йлович Бу́тлеров; 15 September 1828 – 17 August 1886) was a Russian chemist, one of the principal creators of the theory of chemical structure (1857–1861 ...
independently prepared trimethylacetic acid and confirmed it was the same product as Fittig had prepared.
:
In 1855, Charles-Adolphe Wurtz
Charles Adolphe Wurtz (; 26 November 181710 May 1884) was an Alsatian French chemist. He is best remembered for his decades-long advocacy for the atomic theory and for ideas about the structures of chemical compounds, against the skeptical opinio ...
showed that when sodium acted upon alkyl iodide
Organoiodine compounds are organic compounds that contain one or more carbon–iodine bonds. They occur widely in organic chemistry, but are relatively rare in nature. The thyroxine hormones are organoiodine compounds that are required for he ...
s, the alkyl
In organic chemistry, an alkyl group is an alkane missing one hydrogen.
The term ''alkyl'' is intentionally unspecific to include many possible substitutions.
An acyclic alkyl has the general formula of . A cycloalkyl is derived from a cycloalk ...
residues combined to form more complex hydrocarbon
In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ex ...
s; Fittig developed this Wurtz reaction
In organic chemistry, the Wurtz reaction, named after Charles Adolphe Wurtz, is a coupling reaction whereby two alkyl halides are treated with sodium metal to form a higher alkane.
: 2 R−X + 2 Na → R−R + 2 NaX
The reaction is of little v ...
method by showing that a mixture of an aryl halide In organic chemistry, an aryl halide (also known as haloarene) is an aromatic compound in which one or more hydrogen atoms, directly bonded to an aromatic ring are replaced by a halide. The haloarene are different from haloalkanes because they exh ...
and an alkyl halide
The haloalkanes (also known as halogenoalkanes or alkyl halides) are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely ...
, under similar treatment, yielded homologues of benzene
Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, ...
. This process is now known as the Wurtz-Fittig reaction.
His investigations on Perkin's reaction led him to an explanation of its mechanism which appeared to be more in accordance with the facts. The question, however, was one of much difficulty, and at the time the exact course of the reaction appears to await solution. These researches incidentally solved the constitution of coumarin
Coumarin () or 2''H''-chromen-2-one is an aromatic organic chemical compound with formula . Its molecule can be described as a benzene molecule with two adjacent hydrogen atoms replaced by a lactone-like chain , forming a second six-membered h ...
, the odoriferous principle of woodruff. Fittig and Erdmann Erdmann is a first name and surname, and may refer to:
Surname
*Carl Erdmann (1898—1945), German historian
*Eduard Erdmann (1896—1958), Baltic German pianist and composer
*Hans Otto Erdmann (1896–1944), member of the German resistance
*Hugo E ...
's observation that γ-phenyl structural analog
A structural analog (analogue in modern traditional English; Commonwealth English), also known as a chemical analog or simply an analog, is a compound having a structure similar to that of another compound, but differing from it in respect to a ce ...
of isocrotonic acid
Isocrotonic acid (also known as quartenylic acid; formally named (''Z'')-2-butenoic acid) is the ''cis'' isomer of crotonic acid. It is an oil, possessing a smell similar to that of brown sugar. It boils at 171.9 °C, concomitant with con ...
readily yielded α-naphthol
1-Naphthol, or α-naphthol, is a fluorescent organic compound with the formula . It is a white solid. It is an isomer of 2-naphthol differing by the location of the hydroxyl group on the naphthalene ring. The naphthols are naphthalene homologues ...
by loss of water was of much importance, since it afforded valuable evidence as to the constitution of naphthalene
Naphthalene is an organic compound with formula . It is the simplest polycyclic aromatic hydrocarbon, and is a white crystalline solid with a characteristic odor that is detectable at concentrations as low as 0.08 ppm by mass. As an aromati ...
. They also investigated certain hydrocarbons occurring in the high boiling point fraction of the coal tar
Coal tar is a thick dark liquid which is a by-product of the production of coke and coal gas from coal. It is a type of creosote. It has both medical and industrial uses. Medicinally it is a topical medication applied to skin to treat psoriasi ...
distillate
Distillation, or classical distillation, is the process of separating the components or substances from a liquid mixture by using selective boiling and condensation, usually inside an apparatus known as a still. Dry distillation is the heat ...
and solved the constitution of phenanthrene
Phenanthrene is a polycyclic aromatic hydrocarbon (PAH) with formula C14H10, consisting of three fused benzene rings. It is a colorless, crystal-like solid, but can also appear yellow. Phenanthrene is used to make dyes, plastics and pesticides, e ...
. Much initial knowledge of the alkaloid piperine
Piperine, along with its isomer chavicine, is the alkaloid responsible for the pungency of black pepper and long pepper. It has been used in some forms of traditional medicine.
Preparation
Due to its poor solubility in water, piperine is typica ...
was owed to Fittig, who in collaboration with Ira Remsen
Ira Remsen (February 10, 1846 – March 4, 1927) was an American chemist who discovered the artificial sweetener saccharin along with Constantin Fahlberg. He was the second president of Johns Hopkins University.
Early life
Ira Remsen was born ...
established its constitution in 1871.[
Fittig published two widely used textbooks; be edited several editions of Wohler's ''Grundriss der organischen Chemie'' (11th ed., 1887) and wrote an ''Unorganische Chemie'' (1st ed., 1872; 3rd, 1882). His researches were recognized by many scientific societies and institutions, the Royal Society awarding him the Davy medal in 1906.][
]
See also
*2,5-Furandicarboxylic acid
2,5-Furandicarboxylic acid (FDCA) is an organic chemical compound consisting of two carboxylic acid groups attached to a central furan ring. It was first reported as ''dehydromucic acid'' by Rudolph Fittig and Heinzelmann in 1876, who produced it v ...
*Durene
Durene, or 1,2,4,5-tetramethylbenzene, is an organic compound with the formula C6H2(CH3)4. It is a colourless solid with a sweet odor. The compound is classified as an alkylbenzene. It is one of three isomers of tetramethylbenzene, the other t ...
*Pinacol coupling reaction A pinacol coupling reaction is an organic reaction in which a carbon–carbon bond is formed between the carbonyl groups of an aldehyde or a ketone in presence of an electron donor in a free radical process. The reaction product is a vicinal diol. ...
References
Sources
*
External links
Genealogy database entry, University of Illinois
{{DEFAULTSORT:Fittig, Whilhelm Rudolph
1835 births
1910 deaths
19th-century German chemists
20th-century German chemists
Scientists from Hamburg
19th-century German inventors
Members of the Göttingen Academy of Sciences and Humanities