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1,2-Wittig Rearrangement
A 1,2-Wittig rearrangement is a categorization of chemical reactions in organic chemistry, and consists of a 1,2-rearrangement of an ether with an alkyllithium compound. The reaction is named for Nobel Prize winning chemist Georg Wittig. : \mathsf The intermediate product is an alkoxy lithium salt and the final product an alcohol. When R" is a good leaving group and electron withdrawing group such as a cyanide (CN) group,''Preparation of aryl benzyl ketones by ,2Wittig rearrangement'' Alan R. Katritzky, Yuming Zhang, Sandeep K. Singh Arkivoc pp. 146–50 2002 (viilink this group is eliminated and the corresponding ketone is formed. : \mathsf Reaction mechanism The reaction mechanism centers on the formation of a free radical pair with lithium migrating from the carbon atom to the oxygen atom. The R radical then recombines with the ketyl.''Wittig Rearrangement of Lithiated Allyl Aryl Ethers: A Mechanistic Study'' Sven Strunk, Manfred Schlosser European Journal of Organic Chemi ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organic Reaction
Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic reactions, rearrangement reactions, photochemical reactions and redox reactions. In organic synthesis, organic reactions are used in the construction of new organic molecules. The production of many man-made chemicals such as drugs, plastics, food additives, fabrics depend on organic reactions. The oldest organic reactions are combustion of organic fuels and saponification of fats to make soap. Modern organic chemistry starts with the Wöhler synthesis in 1828. In the history of the Nobel Prize in Chemistry awards have been given for the invention of specific organic reactions such as the Grignard reaction in 1912, the Diels-Alder reaction in 1950, the Wittig reaction in 1979 and olefin metathesis in 2005. Classifications Organic chemistry has a strong tradition of naming a specific reacti ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ketyl
A ketyl group in organic chemistry is an anion radical that contains a group R2C−O•. It is the product of the 1-electron reduction of a ketone. Another mesomeric structure has the radical position on carbon and the negative charge on oxygen. : Ketyls can be formed as radical anions by one-electron reduction of carbonyls with alkali metals. Sodium and potassium metal reduce benzophenone in THF solution to the soluble ketyl radical. Ketyls are also invoked as intermediates in the pinacol coupling reaction. Reactions Water The ketyl radicals derived from the reaction of sodium and benzophenone is a common laboratory desiccant. Ketyls react quickly with the water, peroxides, and with oxygen. Thus, the deep purple coloration qualitatively indicates dry, peroxide-free, and oxygen-free conditions. The method for drying is still popular in many laboratories due to its ability to produce such pure solvent quickly. An alternative option for chemists interested only in water ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Rearrangement Reactions
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 curved ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Smiles Rearrangement
The Smiles rearrangement is an organic reaction and a rearrangement reaction named after British chemist Samuel Smiles. It is an intramolecular nucleophilic aromatic substitution of the type: where X in the arene compound can be a sulfone, a sulfide, an ether or any substituent capable of dislodging from the arene carrying a negative charge. The terminal functional group in the chain end Y is able to act as a strong nucleophile for instance an alcohol, amine or thiol. As in other nucleophilic aromatic substitutions the arene requires activation by an electron-withdrawing group preferably in the aromatic ortho position. In one modification called the Truce–Smiles rearrangement the incoming nucleophile is sufficiently strong that the arene does not require this additional activation, for example when the nucleophile is an organolithium. This reaction is exemplified by the conversion of an aryl sulfone into a sulfinic acid by action of ''n''-butyllithium: This particular reac ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
2,3-Wittig Rearrangement
The ,3Wittig rearrangement is the transformation of an allylic ether into a homoallylic alcohol via a concerted, pericyclic process. Because the reaction is concerted, it exhibits a high degree of stereocontrol, and can be employed early in a synthetic route to establish stereochemistry. The Wittig rearrangement requires strongly basic conditions, however, as a carbanion intermediate is essential. ,2Wittig rearrangement is a competitive process. Introduction ,3Sigmatropic rearrangements occur for a variety of groups X and Y (see below). When X is a carbanion and Y an alkoxide, the rearrangement is called the ,3Wittig rearrangement and the products are pent-1-en-5-ols. The ,2Wittig rearrangement, which produces isomeric pent-5-en-1-ols, is a competitive process that takes place at high temperatures. Because of the high atom economy and stereoselectivity of the ,3rearrangement, it has gained considerable synthetic utility. The carbanion is generated by direct lithiation of m ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Dyotropic Reaction
A dyotropic reaction (from the Greek ''dyo'', meaning two) in organic chemistry is a type of organic reaction and more specifically a pericyclic valence isomerization in which two sigma bonds simultaneously migrate intramolecularly. The reaction type is of some relevance to organic chemistry because it can explain how certain reactions occur and because it is a synthetic tool in the synthesis of organic molecules for example in total synthesis. It was first described by Manfred T. Reetz in 1971 In a type I reaction two migrating groups interchange their relative positions and a type II reaction involves migration to new bonding sites without positional interchange. Type I rearrangements In type I rearrangements (Y-A-B-X conversion to X-A-B-Y) the two migrating groups are oriented trans to each other and as a result of the rearrangement they migrate to opposite sides. The first example of a dyotropic rearrangement involving a carbon-carbon bond was reported by Cyril A. Grob ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Meisenheimer Complex
A Meisenheimer complex or Jackson–Meisenheimer complex in organic chemistry is a 1:1 reaction adduct between an arene carrying electron withdrawing groups and a nucleophile. These complexes are found as reactive intermediates in nucleophilic aromatic substitution but stable and isolated Meisenheimer salts are also known. Background The early development of this type of complex takes place around the turn of the 19th century. In 1886 Janovski observed an intense violet color when he mixed ''meta''-dinitrobenzene with an alcoholic solution of alkali. In 1895 Cornelis Adriaan Lobry van Troostenburg de Bruyn investigated a red substance formed in the reaction of trinitrobenzene with potassium hydroxide in methanol. In 1900 Jackson and Gazzolo reacted trinitroanisole with sodium methoxide and proposed a quinoid structure for the reaction product. : In 1902 Jakob Meisenheimer observed that by acidifying their reaction product, the starting material was recovered. With three electron ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Trimethylsilyl Chloride
Trimethylsilyl chloride, also known as chlorotrimethylsilane is an organosilicon compound (silyl halide), with the formula (CH3)3SiCl, often abbreviated Me3SiCl or TMSCl. It is a colourless volatile liquid that is stable in the absence of water. It is widely used in organic chemistry. Preparation TMSCl is prepared on a large scale by the ''direct process'', the reaction of methyl chloride with a silicon-copper alloy. The principal target of this process is dimethyldichlorosilane, but substantial amounts of the trimethyl and monomethyl products are also obtained. The relevant reactions are (Me = CH3): : x MeCl + Si → Me3SiCl, Me2SiCl2, MeSiCl3, other products Typically about 2–4% of the product stream is the monochloride, which forms an azeotrope with MeSiCl3. Reactions and uses TMSCl is reactive toward nucleophiles, resulting in the replacement of the chloride. In a characteristic reaction of TMSCl, the nucleophile is water, resulting in hydrolysis to give the hexameth ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Retention Of Configuration
Walden inversion is the inversion of a stereogenic center in a chiral molecule in a chemical reaction. Since a molecule can form two enantiomers around a stereogenic center, the Walden inversion converts the configuration of the molecule from one enantiomeric form to the other. For example, in an SN2 reaction, Walden inversion occurs at a tetrahedral carbon atom. It can be visualized by imagining an umbrella turned inside-out in a gale. In the Walden inversion, the backside attack by the nucleophile in an SN2 reaction gives rise to a product whose configuration is opposite to the reactant. Therefore, during SN2 reaction, 100% inversion of product takes place. This is known as Walden inversion. It was first observed by chemist Paul Walden in 1896. He was able to convert one enantiomer of a chemical compound into the other enantiomer and back again in a so-called Walden cycle which went like this: (+) chlorosuccinic acid (1 in the illustration) was converted to (+) malic ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Cage Effect (chemistry)
In chemistry, the cage effect (also known as geminate recombination) describes how the properties of a molecule are affected by its surroundings. First introduced by Franck and Rabinowitch in 1934, the cage effect suggests that instead of acting as an individual particle, molecules in solvent are more accurately described as an encapsulated particle. The encapsulated molecules or radicals are called cage pairs or geminate pairs. In order to interact with other molecules, the caged particle must diffuse from its solvent cage. The typical lifetime of a solvent cage is 10 seconds. Many manifestations of the cage effect exist. In free radical polymerization, radicals formed from the decomposition of an initiator molecule are surrounded by a cage consisting of solvent and/or monomer molecules. Within the cage, the free radicals undergo many collisions leading to their recombination or mutual deactivation. This can be described by the following reaction: : R\!-\!R \;\;\unders ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
