Fischer–Hepp Rearrangement
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Fischer–Hepp Rearrangement
The Fischer–Hepp rearrangement is a rearrangement reaction in which an aromatic N-nitroso or nitrosamine converts to a carbon nitroso compound: This organic reaction was first described by the German chemist Otto Philipp Fischer (1852–1932) and Eduard Hepp (June 11, 1851 – June 18, 1917) W Pötsch. ''Lexikon bedeutender Chemiker'' (VEB Bibliographisches Institut Leipzig, 1989) in 1886, and is of importance because para- NO secondary anilines cannot be prepared in a direct reaction. The rearrangement reaction takes place by reacting the nitrosamine precursor with hydrochloric acid. The chemical yield is generally good under these conditions, but often much poorer if a different acid is used. The exact reaction mechanism is unknown but there is evidence suggesting an intramolecular reaction. Sources''Named Things in Chemical Industry'' See also * Friedel–Crafts alkylation-like reactions: ** Hofmann-Martius rearrangement **Fries rearrangement The Fries rearrangement, n ...
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Otto Philipp Fischer
Otto is a masculine German given name and a surname. It originates as an Old High German short form (variants ''Audo'', ''Odo'', ''Udo'') of Germanic names beginning in ''aud-'', an element meaning "wealth, prosperity". The name is recorded from the 7th century ( Odo, son of Uro, courtier of Sigebert III). It was the name of three 10th-century German kings, the first of whom was Otto I the Great, the first Holy Roman Emperor, founder of the Ottonian dynasty. The Gothic form of the prefix was ''auda-'' (as in e.g. '' Audaþius''), the Anglo-Saxon form was ''ead-'' (as in e.g. ''Eadmund''), and the Old Norse form was '' auð-''. The given name Otis arose from an English surname, which was in turn derived from ''Ode'', a variant form of ''Odo, Otto''. Due to Otto von Bismarck, the given name ''Otto'' was strongly associated with the German Empire in the later 19th century. It was comparatively frequently given in the United States (presumably in German American families) during t ...
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Chemical Yield
In chemistry, yield, also referred to as reaction yield, is a measure of the quantity of moles of a product formed in relation to the reactant consumed, obtained in a chemical reaction, usually expressed as a percentage. Yield is one of the primary factors that scientists must consider in organic and inorganic chemical synthesis processes. In chemical reaction engineering, "yield", "conversion" and "selectivity" are terms used to describe ratios of how much of a reactant was consumed (conversion), how much desired product was formed (yield) in relation to the undesired product (selectivity), represented as X, Y, and S. Definitions In chemical reaction engineering, "yield", "conversion" and "selectivity" are terms used to describe ratios of how much of a reactant has reacted—conversion, how much of a desired product was formed—yield, and how much desired product was formed in ratio to the undesired product—selectivity, represented as X,S, and Y. According to the ''Ele ...
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Fries Rearrangement
The Fries rearrangement, named for the German chemist Karl Theophil Fries, is a rearrangement reaction of a phenolic ester to a hydroxy aryl ketone by catalysis of Lewis acids. It involves migration of an acyl group of phenol ester to the aryl ring. The reaction is ortho and para selective and one of the two products can be favoured by changing reaction conditions, such as temperature and solvent. Mechanism Despite many efforts, a definitive reaction mechanism for the Fries rearrangement has not been determined. Evidence for inter- and intramolecular mechanisms have been obtained by crossover experiments with mixed reactants. The reaction progress is not dependent on solvent or substrate. A widely accepted mechanism involves a carbocation intermediate. In the first reaction step a Lewis acid for instance aluminium chloride co-ordinates to the carbonyl oxygen atom of the acyl group. This oxygen atom is more electron rich than the phenolic oxygen atom and is the preferred ...
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Intramolecular Reaction
Intramolecular in chemistry describes a process or characteristic limited within the structure of a single molecule, a property or phenomenon limited to the extent of a single molecule. Examples * intramolecular hydride transfer (transfer of a hydride ion from one part to another within the same molecule) * intramolecular hydrogen bond (a hydrogen bond formed between two functional groups of the same molecule) *cyclization of ω-haloalkylamines and alcohols to form the corresponding saturated nitrogen and oxygen heterocycles, respectively (an SN2 reaction within the same molecule) In intramolecular organic reactions, two reaction sites are contained within a single molecule. This creates a very high effective concentration (resulting in high reaction rates), and, therefore, many intramolecular reactions that would not occur as an intermolecular reaction between two compounds take place. Examples of intramolecular reactions are the Smiles rearrangement, the Dieckmann condensation ...
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Reaction Mechanism
In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical change occurs. A chemical mechanism is a theoretical conjecture that tries to describe in detail what takes place at each stage of an overall chemical reaction. The detailed steps of a reaction are not observable in most cases. The conjectured mechanism is chosen because it is thermodynamically feasible, and has experimental support in isolated intermediates (see next section) or other quantitative and qualitative characteristics of the reaction. It also describes each reactive intermediate, activated complex, and transition state, and which bonds are broken (and in what order), and which bonds are formed (and in what order). A complete mechanism must also explain the reason for the reactants and catalyst used, the stereochemistry observed in reactants and products, all products formed and the amount of each. The electron or arrow pushing method is often used in i ...
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Acid
In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a sequence of database operations that satisfies the ACID properties (which can be perceived as a single logical operation on the data) is called a ''transaction''. For example, a transfer of funds from one bank account to another, even involving multiple changes such as debiting one account and crediting another, is a single transaction. In 1983, Andreas Reuter and Theo Härder coined the acronym ''ACID'', building on earlier work by Jim Gray who named atomicity, consistency, and durability, but not isolation, when characterizing the transaction concept. These four properties are the major guarantees of the transaction paradigm, which has influenced many aspects of development in database systems. According to Gray and Reuter, the IBM Informa ...
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Hydrochloric Acid
Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid Acid strength is the tendency of an acid, symbolised by the chemical formula HA, to dissociate into a proton, H+, and an anion, A-. The dissociation of a strong acid in solution is effectively complete, except in its most concentrated solutions .... It is a component of the gastric acid in the digestive systems of most animal species, including humans. Hydrochloric acid is an important laboratory reagent and industrial chemical. History In the early tenth century, the Persian physician and alchemist Abu Bakr al-Razi ( 865–925, Latin: Rhazes) conducted experiments with sal ammoniac (ammonium chloride) and vitriol (hydrated sulfates of various metals), which he distilled together, thus producing the gas hydrogen chloride. In doing so, al-Razi may have stumbled upon a primitive method ...
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Rearrangement Reaction
In organic chemistry, a rearrangement reaction is a broad class of organic reactions where the carbon skeleton of a molecule is rearranged to give a structural isomer of the original molecule. Often a substituent moves from one atom to another atom in the same molecule, hence these reactions are usually intramolecular. In the example below, the substituent R moves from carbon atom 1 to carbon atom 2: :\underset\ce\ce\underset\ce\ce Intermolecular rearrangements also take place. A rearrangement is not well represented by simple and discrete electron transfers (represented by curved arrows in organic chemistry texts). The actual mechanism of alkyl groups moving, as in Wagner-Meerwein rearrangement, probably involves transfer of the moving alkyl group fluidly along a bond, not ionic bond-breaking and forming. In pericyclic reactions, explanation by orbital interactions give a better picture than simple discrete electron transfers. It is, nevertheless, possible to draw the curv ...
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Aniline
Aniline is an organic compound with the formula C6 H5 NH2. Consisting of a phenyl group attached to an amino group, aniline is the simplest aromatic amine In organic chemistry, an aromatic amine is an organic compound consisting of an aromatic ring attached to an amine. It is a broad class of compounds that encompasses aniline Aniline is an organic compound with the formula C6 H5 NH2. Consi .... It is an industrially significant Commodity chemicals, commodity chemical, as well as a versatile starting material for fine chemical synthesis. Its main use is in the manufacture of precursors to polyurethane, dyes, and other industrial chemicals. Like most volatile amines, it has the odor of rotten fish. It Combustion, ignites readily, burning with a smoky flame characteristic of aromatic compounds. It is toxic to humans. Relative to benzene, it is electron-rich. It thus participates more rapidly in electrophilic aromatic substitution reactions. Likewise, it is also prone ...
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Aromatic Para Substituent
Arene substitution patterns are part of organic chemistry IUPAC nomenclature and pinpoint the position of substituents other than hydrogen in relation to each other on an aromatic hydrocarbon. ''Ortho'', ''meta'', and ''para'' substitution * In ''ortho''-substitution, two substituents occupy positions next to each other, which may be numbered 1 and 2. In the diagram, these positions are marked R and ''ortho''. * In ''meta''-substitution the substituents occupy positions 1 and 3 (corresponding to R and ''meta'' in the diagram). * In ''para''-substitution, the substituents occupy the opposite ends (positions 1 and 4, corresponding to R and ''para'' in the diagram). The toluidines serve as an example for these three types of substitution. Synthesis Electron donating groups, for example amino, hydroxyl, alkyl, and phenyl groups tend to be ''ortho''/''para''-directors, and electron withdrawing groups such as nitro, nitrile, and ketone groups, tend to be ''meta''-directors. Propert ...
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