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Dowd–Beckwith Ring-expansion Reaction
The Dowd–Beckwith ring-expansion reaction is an organic reaction in which a cyclic β- keto ester is expanded by up to 4 carbons in a free radical ring expansion reaction through an α-alkylhalo substituent. The radical initiator system is based on AIBN and tributyltin hydride. The cyclic β- keto ester can be obtained through a Dieckmann condensation. The original reaction consisted of a nucleophilic aliphatic substitution of the enolate of ethyl cyclohexanone-2-carboxylate with 1,4-diiodobutane and sodium hydride followed by ring expansion to ethyl cyclodecanone-6-carboxylate. A side-reaction is organic reduction of the iodoalkane. center, Dowd–Beckwith Ring Expansion.gif Reaction mechanism The reaction mechanism involves a bicyclic intermediate. The reaction is initiated by thermal decomposition of AIBN. The resulting radicals abstract hydrogen from tributyltin hydride to a tributyltin radical which in turn abstracts the halogen atom to form an alkyl radical. This r ... [...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 spe ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Activation Energy
In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol). Activation energy can be thought of as the magnitude of the potential barrier (sometimes called the energy barrier) separating minima of the potential energy surface pertaining to the initial and final thermodynamic state. For a chemical reaction to proceed at a reasonable rate, the temperature of the system should be high enough such that there exists an appreciable number of molecules with translational energy equal to or greater than the activation energy. The term "activation energy" was introduced in 1889 by the Swedish scientist Svante Arrhenius. Other uses Although less commonly used, activation energy also applies to nuclear reactions and various other physical phenomena. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Deuterium
Deuterium (or hydrogen-2, symbol or deuterium, also known as heavy hydrogen) is one of two stable isotopes of hydrogen (the other being protium, or hydrogen-1). The nucleus of a deuterium atom, called a deuteron, contains one proton and one neutron, whereas the far more common protium has no neutrons in the nucleus. Deuterium has a natural abundance in Earth's oceans of about one atom of deuterium among all atoms of hydrogen (see heavy water). Thus deuterium accounts for approximately 0.0156% by number (0.0312% by mass) of all the naturally occurring hydrogen in the oceans, while protium accounts for more than 99.98%. The abundance of deuterium changes slightly from one kind of natural water to another (see Vienna Standard Mean Ocean Water). ( Tritium is yet another hydrogen isotope, with two neutrons, that is far more rare and is radioactive.) The name ''deuterium'' is derived from the Greek , meaning "second", to denote the two particles composing the nucleus. De ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Catalytic Cycle
In chemistry, a catalytic cycle is a multistep reaction mechanism that involves a catalyst. The catalytic cycle is the main method for describing the role of catalysts in biochemistry, organometallic chemistry, bioinorganic chemistry, materials science, etc. Since catalysts are regenerated, catalytic cycles are usually written as a sequence of chemical reactions in the form of a loop. In such loops, the initial step entails binding of one or more reactants by the catalyst, and the final step is the release of the product and regeneration of the catalyst. Articles on the Monsanto process, the Wacker process, and the Heck reaction show catalytic cycles. A catalytic cycle is not necessarily a full reaction mechanism. For example, it may be that the intermediates have been detected, but it is not known by which mechanisms the actual elementary reactions occur. Precatalysts Precatalysts are not catalysts but are ''precursors'' to catalysts. Precatalysts are converted in the re ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 ... [...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-free ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Bicyclic
In chemistry, a bicyclic molecule () is a molecule that features two joined rings. Bicyclic structures occur widely, for example in many biologically important molecules like α-thujene and camphor. A bicyclic compound can be carbocyclic (all of the ring atoms are carbons), or heterocyclic (the rings' atoms consist of at least two elements), like DABCO. Moreover, the two rings can both be aliphatic (''e.g.'' decalin and norbornane), or can be aromatic (''e.g.'' naphthalene), or a combination of aliphatic and aromatic (''e.g.'' tetralin). Three modes of ring junction are possible for a bicyclic compound: * In spirocyclic compounds, the two rings share only one single atom, the spiro atom, which is usually a quaternary carbon. An example of a spirocyclic compound is the photochromic switch spiropyran. * In fused/condensed bicyclic compounds, two rings share two adjacent atoms. In other words, the rings share one covalent bond, ''i.e.'' the so-called bridgehead atoms are di ... [...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 su ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 cycloalkane by removal of a hydrogen atom from a ring and has the general formula . Typically an alkyl is a part of a larger molecule. In structural formulae, the symbol R is used to designate a generic (unspecified) alkyl group. The smallest alkyl group is methyl, with the formula . Related concepts Alkylation is an important operation in refineries, for example in the production of high-octane gasoline. Alkylating antineoplastic agents are a class of compounds that are used to treat cancer. In such case, the term alkyl is used loosely. For example, nitrogen mustards are well-known alkylating agents, but they are not simple hydrocarbons. In chemistry, alkyl is a group, a substituent, that is attached to other molecular fragments. Fo ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Halogen
The halogens () are a group in the periodic table consisting of five or six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), and tennessine (Ts). In the modern IUPAC nomenclature, this group is known as group 17. The word "halogen" means "salt former" (or "salt maker"). When halogens react with metals, they produce a wide range of salts, including calcium fluoride, sodium chloride (common table salt), silver bromide and potassium iodide. The group of halogens is the only periodic table group that contains elements in three of the main states of matter at standard temperature and pressure. All of the halogens form acids when bonded to hydrogen. Most halogens are typically produced from minerals or salts. The middle halogens—chlorine, bromine, and iodine—are often used as disinfectants. Organobromides are the most important class of flame retardants, while elemental halogens are dangerous and can be toxic. His ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
