|
Trimethylenemethane Cycloaddition
Trimethylenemethane cycloaddition is the formal +2annulation of trimethylenemethane (TMM) derivatives to two-atom pi systems. Although TMM itself is too reactive and unstable to be stored, reagents which can generate TMM or TMM synthons ''in situ'' can be used to effect cycloaddition reactions with appropriate electron acceptors. Generally, electron-deficient pi bonds undergo cyclization with TMMs more easily than electron-rich pi bonds. Introduction Trimethylenemethane is a neutral, four-carbon molecule composed of four pi bonds; thus, it must be expressed either as a non-Kekulé molecule or a zwitterion. The orbital energy levels of TMM reveal that it possesses singlet and triplet states; generally, these states exhibit different reactivity and selectivity profiles. A singlet +2cycloaddition, when it is concerted, is believed to proceed under frontier orbital control. When electron-rich TMMs are involved, the ''A'' orbital serves as the HOMO (leading to fused products if the TM ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Annulation
In organic chemistry annulation (from the Latin ''anellus'' for "little ring"; occasionally annelation) is a chemical reaction in which a new ring is constructed on a molecule. : Examples are the Robinson annulation, Danheiser annulation and certain cycloadditions. Annular molecules are constructed from side-on condensed cyclic segments, for example helicenes and acenes. In transannulation a bicyclic molecule is created by intramolecular carbon-carbon bond formation in a large monocyclic ring. An example is the samarium(II) iodide induced ketone - alkene cyclization of ''5-methylenecyclooctanone'' which proceeds through a ketyl intermediate: : Benzannulation The term benzannulated compounds refers to derivatives of cyclic compounds (usually aromatic) which are fused to a benzene ring. Examples are listed in the table below: In contemporary chemical literature, the term benzannulation also means "construction of benzene rings from acyclic precursors". upright=1.4, Protonatio ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Stepwise Reaction
In chemistry, a stepwise reaction (also called an overall reaction, complex reaction, and multistep reaction, among others) is a chemical reaction with one or more reaction intermediates, which by definition involves at least two consecutive elementary reactions. In a stepwise reaction, not all bonds are broken and formed at the same time. Hence, intermediates appear in the reaction pathway going from the reactants to the products. A stepwise reaction distinguishes itself from an elementary reaction in which the transformation is assumed to occur in a single step and to pass through a single transition state. In contrast to elementary reactions which follow the law of mass action, the rate law of stepwise reactions is obtained by combining the rate laws of the multiple elementary steps, and can become rather complex. Moreover, when speaking about catalytic reactions, the diffusion may also limit the reaction. In general, however, there is one very slow step, which is the rate-de ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Methylene Group
In organic chemistry, a methylene group is any part of a molecule that consists of two hydrogen atoms bound to a carbon atom, which is connected to the remainder of the molecule by two single bonds. The group may be represented as , where the '<' denotes the two bonds. This can equally well be represented as . This stands in contrast to a situation where the carbon atom is bound to the rest of the molecule by a double bond, which is preferably called a , represented . Formerly the methylene name was used for both isomers. The name ““ can be used for the single-bonded isomer, to emphatically exclude methylidene. The distinction is often important, because the double bond is chemically di ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Alkene
In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond. Alkene is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds.H. Stephen Stoker (2015): General, Organic, and Biological Chemistry'. 1232 pages. Two general types of monoalkenes are distinguished: terminal and internal. Also called α-olefins, terminal alkenes are more useful. However, the International Union of Pure and Applied Chemistry (IUPAC) recommends using the name "alkene" only for acyclic hydrocarbons with just one double bond; alkadiene, alkatriene, etc., or polyene for acyclic hydrocarbons with two or more double bonds; cycloalkene, cycloalkadiene, etc. for cyclic ones; and "olefin" for the general class – cyclic or acyclic, with one or more double bonds. Acyclic alkenes, with only one double bond and no other functional groups (also known as mono-enes) form a homologous series of hydrocarbons with the general formula with '' ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 recycles quickly, very small amounts of catalyst often suffice; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process of regenerating the catalyst. Catalysis may be classified as either homogeneous, whose components are dispersed in the same phase (usually gaseous or liquid) as the reactant, or heterogeneous, whose components are not in the same phase. Enzymes and other biocatalysts are often considered as a third category. Catalysis is ubiquitous in chemical industry of all kinds. Estimates are that 90% of all commercially produced chemical products involve catalysts at some s ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Transition Metal
In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can use d orbitals as valence orbitals to form chemical bonds. The lanthanide and actinide elements (the f-block) are called inner transition metals and are sometimes considered to be transition metals as well. Since they are metals, they are lustrous and have good electrical and thermal conductivity. Most (with the exception of group 11 and group 12) are hard and strong, and have high melting and boiling temperatures. They form compounds in any of two or more different oxidation states and bind to a variety of ligands to form coordination complexes that are often coloured. They form many useful alloys and are often employed as catalysts in elemental form or in compounds such as coordination complexes and oxides. Most are strongly param ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Acetate
An acetate is a salt (chemistry), salt formed by the combination of acetic acid with a base (e.g. Alkali metal, alkaline, Alkaline earth metal, earthy, Transition metal, metallic, nonmetallic or radical Radical (chemistry), base). "Acetate" also describes the conjugate acid, conjugate base or ion (specifically, the negatively charged ion called an anion) typically found in aqueous solution and written with the chemical formula . The neutral molecules formed by the combination of the acetate ion and a ''positive'' ion (called a cation) are also commonly called "acetates" (hence, ''acetate of lead'', ''acetate of aluminum'', etc.). The simplest of these is hydrogen acetate (called acetic acid) with corresponding salts, esters, and the polyatomic ion, polyatomic anion , or . Most of the approximately 5 billion kilograms of acetic acid produced annually in industry are used in the production of acetates, which usually take the form of polymers. In nature, acetate is the most common ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Allyl
In organic chemistry, an allyl group is a substituent with the structural formula , where R is the rest of the molecule. It consists of a methylene bridge () attached to a vinyl group (). The name is derived from the scientific name for garlic, . In 1844, Theodor Wertheim isolated an allyl derivative from garlic oil and named it "". The term allyl applies to many compounds related to , some of which are of practical or of everyday importance, for example, allyl chloride. Allylation is any chemical reaction that adds an allyl group to a substrate. Nomenclature A site adjacent to the unsaturated carbon atom is called the allylic position or allylic site. A group attached at this site is sometimes described as allylic. Thus, "has an allylic hydroxyl group". Allylic C−H bonds are about 15% weaker than the C−H bonds in ordinary sp3 carbon centers and are thus more reactive. Benzylic and allylic are related in terms of structure, bond strength, and reactivity. Other re ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Diazene
Diimide, also called diazene or diimine, is a compound having the formula (NH)2. It exists as two geometric isomers, ''E'' (''trans'') and ''Z'' (''cis''). The term diazene is more common for organic derivatives of diimide. Thus, azobenzene is an example of an organic diazene. Synthesis A traditional route to diimide involves oxidation of hydrazine with hydrogen peroxide or air. Alternatively the hydrolysis of diethyl azodicarboxylate or azodicarbonamide affords diimide: :(NCOOH)2 → (NH)2 + 2 CO2 Nowadays, diimide is generated by thermal decomposition of 2,4,6‐triisopropylbenzenesulfonylhydrazide. Because of its instability, diimide is generated and used ''in-situ''. A mixture of both the ''cis'' (''Z-'') and ''trans'' (''E-'') isomers is produced. Both isomers are unstable, and they undergo a slow interconversion. The ''trans'' isomer is more stable, but the ''cis'' isomer is the one that reacts with unsaturated substrates, therefore the equilibrium between them sh ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Dimer (chemistry)
A dimer () ('' di-'', "two" + ''-mer'', "parts") is an oligomer consisting of two monomers joined by bonds that can be either strong or weak, covalent or intermolecular. Dimers also have significant implications in polymer chemistry, inorganic chemistry, and biochemistry. The term ''homodimer'' is used when the two molecules are identical (e.g. A–A) and ''heterodimer'' when they are not (e.g. A–B). The reverse of dimerization is often called dissociation. When two oppositely charged ions associate into dimers, they are referred to as ''Bjerrum pairs'', after Niels Bjerrum. Noncovalent dimers Anhydrous carboxylic acids form dimers by hydrogen bonding of the acidic hydrogen and the carbonyl oxygen. For example, acetic acid forms a dimer in the gas phase, where the monomer units are held together by hydrogen bonds. Under special conditions, most OH-containing molecules form dimers, e.g. the water dimer. Excimers and exciplexes are excited structures with a short lifetime. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ring Strain
In organic chemistry, ring strain is a type of instability that exists when bonds in a molecule form angles that are abnormal. Strain is most commonly discussed for small rings such as cyclopropanes and cyclobutanes, whose internal angles are substantially smaller than the idealized value of approximately 109°. Because of their high strain, the heat of combustion for these small rings is elevated. Ring strain results from a combination of angle strain, conformational strain or Pitzer strain (torsional eclipsing interactions), and transannular strain, also known as van der Waals strain or Prelog strain. The simplest examples of angle strain are small cycloalkanes such as cyclopropane and cyclobutane. Ring strain energy can be attributed to the energy required for the distortion of bond and bond angles in order to close a ring. Ring strain energy is believed to be the cause of accelerated rates in altering ring reactions. Its interactions with traditional bond energies chan ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
