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Fischer Indole Synthesis
The Fischer indole synthesis is a chemical reaction that produces the aromatic heterocycle indole from a (substituted) phenylhydrazine and an aldehyde or ketone under acidic conditions. The reaction was discovered in 1883 by Emil Fischer. Today antimigraine drugs of the triptan class are often synthesized by this method. This reaction can be catalyzed by Brønsted acids such as HCl, H2SO4, polyphosphoric acid and p-toluenesulfonic acid or Lewis acids such as boron trifluoride, zinc chloride, iron chloride, and aluminium chloride. Several reviews have been published. Reaction mechanism The reaction of a (substituted) phenylhydrazine with a carbonyl (aldehyde or ketone) initially forms a phenylhydrazone which isomerizes to the respective enamine (or 'ene-hydrazine'). After protonation, a cyclic ,3sigmatropic rearrangement occurs producing an imine. The resulting imine forms a cyclic aminoacetal (or ''aminal''), which under acid catalysis eliminates NH3, resulting in the ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Hermann Emil Fischer
Hermann Emil Louis Fischer (; 9 October 1852 – 15 July 1919) was a German chemist and 1902 recipient of the Nobel Prize in Chemistry. He discovered the Fischer esterification. He also developed the Fischer projection, a symbolic way of drawing asymmetric carbon atoms. He also hypothesized lock and key mechanism of enzyme action. He never used his first given name, and was known throughout his life simply as Emil Fischer. Early years and career Fischer was born in Euskirchen, near Cologne, the son of Laurenz Fischer, a businessman, and his wife Julie Poensgen. After graduating he wished to study natural sciences, but his father compelled him to work in the family business until determining that his son was unsuitable. Fischer then attended the University of Bonn in 1871, but switched to the University of Strasbourg in 1872. He earned his doctorate in 1874 under Adolf von Baeyer with his study of phthaleins, and was appointed to a position at the university. After eight ye ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Lewis Acid
A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any species that has a filled orbital containing an electron pair which is not involved in bonding but may form a dative bond with a Lewis acid to form a Lewis adduct. For example, NH3 is a Lewis base, because it can donate its lone pair of electrons. Trimethylborane (Me3B) is a Lewis acid as it is capable of accepting a lone pair. In a Lewis adduct, the Lewis acid and base share an electron pair furnished by the Lewis base, forming a dative bond. In the context of a specific chemical reaction between NH3 and Me3B, a lone pair from NH3 will form a dative bond with the empty orbital of Me3B to form an adduct NH3•BMe3. The terminology refers to the contributions of Gilbert N. Lewis. From p. 142: "We are inclined to think of substances as po ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Aminoacetal
In organic chemistry, an aminal or aminoacetal is a functional group or type of organic compound that has two amine groups attached to the same carbon atom: . (As is customary in organic chemistry, R can represent hydrogen or an alkyl group). A common aminal is bis(dimethylamino)methane, a colorless liquid that is prepared by the reaction of dimethylamine and formaldehyde: : 2 (CH3)2NH + CH2O -> CH3)2NCH2 + H2O Aminals are encountered in, for instance, the Fischer indole synthesis. Several examples exist in nature. Physostigmin.svg, Physostigmine,a highly toxic cholinesterase inhibitor found in the Calabar bean. Hodgkinsine.png, Hodgkinsine, an alkaloid with antiviral, antibacterial and antifungal effects 5,10-methylenetetrahydrofolic acid.svg, 5,10-Methylenetetrahydrofolate, an intermediate in one-carbon metabolism Hexahydro-1,3,5-triazine (), an intermediate in the condensation of formaldehyde and ammonia, tends to degrade to hexamethylene tetraamine. Cyclic amin ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Imine
In organic chemistry, an imine ( or ) is a functional group or organic compound containing a carbon–nitrogen double bond (). The nitrogen atom can be attached to a hydrogen or an organic group (R). The carbon atom has two additional single bonds. Imines are common in synthetic and naturally occurring compounds and they participate in many reactions. Structure For ketimines and aldimines, respectively, the five core atoms (C2C=NX and C(H)C=NX, X = H or C) are coplanar. Planarity results from the sp2-hybridization of the mutually double-bonded carbon and the nitrogen atoms. The C=N distance is 1.29-1.31 Å for nonconjugated imines and 1.35 Å for conjugated imines. By contrast, C-N distances in amines and nitriles are 1.47 and 1.16 Å, respectively. Rotation about the C=N bond is slow. Using NMR spectroscopy, both E- and Z-isomers of aldimines have been detected. Owing to steric effects, the E isomer is favored. Nomenclature and classification The term "imine" was coine ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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-established sigma designation from single carbon–carbon bonds and the Greek word ''tropos'', meaning turn. In this type of rearrangement reaction, a substituent moves from one part of a π-bonded system to another part in an intramolecular reaction with simultaneous rearrangement of the π system. True sigmatropic reactions are usually uncatalyzed, although Lewis acid catalysis is possible. Sigmatropic reactions often have transition-metal catalysts that form intermediates in analogous reactions. The most well-known of the sigmatropic rearrangements are the ,3Cope rearrangement, Claisen rearrangement, Carroll rearrangement, and the Fischer indole synthesis. Overview of sigmatropic shifts Woodward–Hoffman sigmatropic shift nomencla ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Protonation
In chemistry, protonation (or hydronation) is the adding of a proton (or hydron, or hydrogen cation), (H+) to an atom, molecule, or ion, forming a conjugate acid. (The complementary process, when a proton is removed from a Brønsted–Lowry acid, is deprotonation.) Some examples include *The protonation of water by sulfuric acid: *:H2SO4 + H2O H3O+ + *The protonation of isobutene in the formation of a carbocation: *:(CH3)2C=CH2 + HBF4 (CH3)3C+ + *The protonation of ammonia in the formation of ammonium chloride from ammonia and hydrogen chloride: *:NH3( g) + HCl( g) → NH4Cl( s) Protonation is a fundamental chemical reaction and is a step in many stoichiometric and catalytic processes. Some ions and molecules can undergo more than one protonation and are labeled polybasic, which is true of many biological macromolecules. Protonation and deprotonation (removal of a proton) occur in most acid–base reactions; they are the core of most acid–base reaction theories. A Brønst ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Enamine
An enamine is an unsaturated compound derived by the condensation of an aldehyde or ketone with a secondary amine. Enamines are versatile intermediates. : The word "enamine" is derived from the affix ''en''-, used as the suffix of alkene, and the root ''amine''. This can be compared with enol, which is a functional group containing both alkene (''en''-) and alcohol (-''ol''). Enamines are considered to be nitrogen analogs of enols. If one of the nitrogen substituents is a hydrogen atom, H, it is the tautomeric form of an imine. This usually will rearrange to the imine; however there are several exceptions (such as aniline). The enamine-imine tautomerism may be considered analogous to the keto-enol tautomerism. In both cases, a hydrogen atom switches its location between the heteroatom (oxygen or nitrogen) and the second carbon atom. Enamines are both good nucleophiles and good bases. Their behavior as carbon-based nucleophiles is explained with reference to the following reson ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Isomerization
In chemistry, isomerization or isomerisation is the process in which a molecule, polyatomic ion or molecular fragment is transformed into an isomer with a different chemical structure. Enolization is an example of isomerization, as is tautomerization. When the isomerization occurs intramolecularly it may be called a rearrangement reaction. When the activation energy for the isomerization reaction is sufficiently small, both isomers will exist in a temperature-dependent equilibrium with each other. Many values of the standard free energy difference, \Delta G^\circ, have been calculated, with good agreement between observed and calculated data. Examples and applications Alkanes Skeletal isomerization occurs in the cracking process, used in the petrochemical industry. As well as reducing the average chain length, straight-chain hydrocarbons are converted to branched isomers in the process, as illustrated the following reaction of ''n''-butane to ''i''-butane. :\overset -> \o ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Phenylhydrazone
Hydrazones are a class of organic compounds with the structure . They are related to ketones and aldehydes by the replacement of the oxygen =O with the = functional group. They are formed usually by the action of hydrazine on ketones or aldehydes. Synthesis Hydrazine, organohydrazines, and 1,1-diorganohydrazines react with aldehydes and ketones to give hydrazones. : Phenylhydrazine reacts with reducing sugars to form hydrazones known as osazones, which was developed by German chemist Emil Fischer as a test to differentiate monosaccharides. Uses Hydrazones are the basis for various analyses of ketones and aldehydes. For example, dinitrophenylhydrazine coated onto a silica sorbent is the basis of an adsorption cartridge. The hydrazones are then eluted and analyzed by HPLC using a UV detector. The compound carbonyl cyanide-''p''-trifluoromethoxyphenylhydrazone (abbreviated as FCCP) is used to uncouple ATP synthesis and reduction of oxygen in oxidative phosphorylation in molec ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 carbonyl group is often referred to as a carbonyl compound. The term carbonyl can also refer to carbon monoxide as a ligand in an inorganic or organometallic complex (a metal carbonyl, e.g. nickel carbonyl). The remainder of this article concerns itself with the organic chemistry definition of carbonyl, where carbon and oxygen share a double bond. Carbonyl compounds In organic chemistry, a carbonyl group characterizes the following types of compounds: Other organic carbonyls are urea and the carbamates, the derivatives of acyl chlorides chloroformates and phosgene, carbonate esters, thioesters, lactones, lactams, hydroxamates, and isocyanates. Examples of inorganic carbonyl compounds are carbon dioxide and carbonyl sulfide. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Hydrazine
Hydrazine is an inorganic compound with the chemical formula . It is a simple pnictogen hydride, and is a colourless flammable liquid with an ammonia-like odour. Hydrazine is highly toxic unless handled in solution as, for example, hydrazine hydrate (). Hydrazine is mainly used as a foaming agent in preparing polymer foams, but applications also include its uses as a precursor to polymerization catalysts, pharmaceuticals, and agrochemicals, as well as a long-term storable propellant for in-space spacecraft propulsion. Additionally, hydrazine is used in various rocket fuels and to prepare the gas precursors used in air bags. Hydrazine is used within both nuclear and conventional electrical power plant steam cycles as an oxygen scavenger to control concentrations of dissolved oxygen in an effort to reduce corrosion. the world hydrazine hydrate market amounted to $350 million. About two million tons of hydrazine hydrate were used in foam blowing agents in 2015. Hydrazines r ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Aluminium Chloride
Aluminium chloride, also known as aluminium trichloride, is an inorganic compound with the formula . It forms hexahydrate with the formula , containing six water molecules of hydration. Both are colourless crystals, but samples are often contaminated with iron(III) chloride, giving a yellow color. The anhydrous material is important commercially. It has a low melting and boiling point. It is mainly produced and consumed in the production of aluminium metal, but large amounts are also used in other areas of the chemical industry. The compound is often cited as a Lewis acid. It is an example of an inorganic compound that reversibly changes from a polymer to a monomer at mild temperature. Structure Anhydrous adopts three structures, depending on the temperature and the state (solid, liquid, gas). Solid has a sheet-like layered structure with cubic close-packed chloride ions. In this framework, the Al centres exhibit octahedral coordination geometry. In contrast, has a more mol ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
