Coarctate Reaction
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Coarctate Reaction
In organic chemistry, a coarctate reaction is a concerted reaction whose transition state involves two rings, in which at least one atom undergoes the simultaneous making and breaking of two bonds. It is an uncommon reaction topology, compared with linear topology and pericyclic topology (itself subdivided into Hückel and Möbius topologies). The name is derived . Transition state topologies Reactions of linear topology are the most common, and consist of all transformations whose transition states are acyclic, including addition, elimination, substitution, and (some types of) fragmentation reactions. By contrast, in pericyclic reactions, the atoms under chemical change form a single closed cycle, and include reactions like the Diels–Alder reaction and Cope rearrangement, among many others. In contrast to these types of reactions, a coarctate reaction is characterized by a doubly cyclic transition state, in which at least one atom undergoes the simultaneous making and b ...
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Transition State Topologies
Transition or transitional may refer to: Mathematics, science, and technology Biology * Transition (genetics), a point mutation that changes a purine nucleotide to another purine (A ↔ G) or a pyrimidine nucleotide to another pyrimidine (C ↔ T) * Transitional fossil, any fossilized remains of a lifeform that exhibits the characteristics of two distinct taxonomic groups * A phase during childbirth contractions during which the cervix completes its dilation Gender and sex * Gender transition, the process of changing one's gender presentation to accord with one's internal sense of one's gender – the idea of what it means to be a man or woman ** Gender-affirming care, the physical aspect of a gender transition ** Gender-affirming surgery, surgical intervention a part of medical gender affirmation Physics * Phase transition, a transformation of the state of matter; for example, the change between a solid and a liquid, between liquid and gas or between gas and plasma * Quantum ...
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Open-chain Compound
In chemistry, an open-chain compound (or open chain compound) or acyclic compound (Greek prefix ''α'' 'without' and ''κύκλος'' 'cycle') is a compound with a linear structure, rather than a Cyclic compound, cyclic one. An open-chain compound having no side groups is called a straight-chain compound (also spelled as straight chain compound). Many of the simple molecules of organic chemistry, such as the alkanes and alkenes, have both linear and ring isomers, that is, both acyclic and cyclic compound, cyclic. For those with 4 or more carbons, the linear forms can have straight-chain or branched-chain isomers. The lowercase prefix ''n-'' denotes the straight-chain isomer; for example, ''n''-butane is straight-chain butane, whereas ''i''-butane is isobutane. Cycloalkanes are isomers of alkenes, not of alkanes, because the ring's closure involves a C-C bond. Having no rings (aromatic or otherwise), all open-chain compounds are aliphatic compound, aliphatic. Typically in biochemistr ...
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Woodward–Hoffmann Rules
The Woodward–Hoffmann rules (or the pericyclic selection rules) are a set of rules devised by Robert Burns Woodward and Roald Hoffmann to rationalize or predict certain aspects of the stereochemistry and activation energy of Pericyclic reaction, pericyclic reactions, an important class of reactions in organic chemistry. The rules originate in certain symmetries of the Molecular orbital, molecule's orbital structure that any molecular Hamiltonian Conserved quantity, conserves. Consequently, any symmetry-violating reaction must Coupling (physics), couple extensively to Thermal bath (thermodynamics), the environment; this imposes an energy barrier on its occurrence, and such reactions are called symmetry-forbidden. Their opposites are symmetry-allowed. Although the symmetry-imposed barrier is often formidable (up to ca. 5 eV or 480 kJ/mol in the case of a forbidden [2+2] cycloaddition), the prohibition is not absolute, and symmetry-forbidden reactions can still take place if other ...
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Dimethyldioxirane
Dimethyldioxirane (DMDO) is the organic compound with the formula . It is the dioxirane derived from acetone and can be viewed as the monomer of acetone peroxide. It is a powerful selective oxidizing agent that finds some use in organic synthesis. It is known only in the form of a dilute solution, usually in acetone, and hence the properties of the pure material are largely unknown. Synthesis DMDO is not commercially available because of chemical instability. DMDO can be prepared as dilute solutions (~0.1 M) by treatment of acetone with potassium peroxymonosulfate , usually in the form of Oxone (2KHSO5·KHSO4·K2SO4). : The preparation of DMDO is rather inefficient (typical yields < 3%) and typically only yields a relatively dilute solution in acetone (only up to approximately 0.1 M). This is tolerable as preparation uses inexpensive substances: acetone, sodium bicarbonate, and oxone. Cold solutions (−10 to −20 °C) of DMDO are stable for days. Decomposition is accelerat ...
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Cope Rearrangement
A cope ( ("rain coat") or ("cape")) is a liturgical long mantle or cloak, open at the front and fastened at the breast with a band or clasp. It may be of any liturgical colour. A cope may be worn by any rank of the Catholic or Anglican clergy, and by licensed lay ministers on certain occasions. If worn by a bishop, it is generally accompanied by a mitre. The clasp, which is often highly ornamented, is called a ''morse''. In art, angels are often shown wearing copes, especially in Early Netherlandish painting. History There has been little change in the character of the cope since it was first worn by the clergy. It was made of a semicircular piece of silk or other material, its shape distinguishing it from the chasuble, which had straight edges sewn together in front. Both garments are similar in form and origin to the Orthodox phelonion. Modern copes no longer have a hood. Some early examples feature a triangular hood, which was intended to protect the head during pro ...
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Diels–Alder Reaction
In organic chemistry, the Diels–Alder reaction is a chemical reaction between a Conjugated system, conjugated diene and a substituted alkene, commonly termed the Diels–Alder reaction#The dienophile, dienophile, to form a substituted cyclohexene derivative. It is the prototypical example of a pericyclic reaction with a concerted reaction, concerted mechanism. More specifically, it is classified as a thermally allowed [4+2] cycloaddition with Woodward–Hoffmann rules, Woodward–Hoffmann symbol [π4s + π2s]. It was first described by Otto Diels and Kurt Alder in 1928. For the discovery of this reaction, they were awarded the Nobel Prize in Chemistry in 1950. Through the simultaneous construction of two new carbon–carbon bonds, the Diels–Alder reaction provides a reliable way to form six-membered rings with good control over the regio- and stereochemical outcomes. Consequently, it has served as a powerful and widely applied tool for the introduction of chemical complexity in ...
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Fragmentation Reaction
Fragmentation or fragmented may refer to: Computers * Fragmentation (computing), a phenomenon of computer storage * File system fragmentation, the tendency of a file system to lay out the contents of files non-continuously * IP fragmentation, a process in computer networking Science * Fragmentation (cell biology), in cells * Fragmentation (reproduction), a form of asexual reproduction * Fragmentation of memory, a psychological disorder * Fragmentation (mass spectrometry), a technique to study structure of molecules * Fragmentation (weaponry), a feature of explosive weaponry * Fragmentation (medicine), an operation that breaks of solid matter in a body part into pieces, such as kidney stones * Fragmentation, the quantification by photoanalysis of blasted material * Hadronization, with quarks Other * Fragmentation (economics), a process of globalization * Fragmentation (music), a compositional technique * Fragmentation (sociology), a term used in urban sociology * Feudal fragmen ...
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Möbius–Hückel Concept
In chemistry, the Möbius–Hückel treatment is a methodology used to predict whether a reaction is allowed or forbidden. It is often used along with the Woodward–Hoffmann approach. The description in this article uses the plus and minus sign notation for parity as shorthand while proceeding around a cycle of orbitals in a molecule or system, while the Woodward–Hoffmann methodology uses a large number of rules with the same consequences. Introduction One year following the Woodward–Hoffmann and Longuet-Higgins–Abrahmson publications, it was noted by Zimmerman that both transition states and stable molecules sometimes involved a Möbius array of basis orbitals. The Möbius–Hückel treatment provides an alternative to the Woodward–Hoffmann one. In contrast to the Woodward–Hoffmann approach the Möbius–Hückel treatment is not dependent on symmetry and only requires counting the number of plus-sign ↔ minus-sign inversions in proceeding around the cyclic array ...
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Organic Chemistry
Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic matter, organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; Greeves, N. and Warren, S. (2012) ''Organic Chemistry''. Oxford University Press. pp. 1–15. . Study of structure determines their structural formula. Study of properties includes Physical property, physical and Chemical property, chemical properties, and evaluation of Reactivity (chemistry), chemical reactivity to understand their behavior. The study of organic reactions includes the organic synthesis, chemical synthesis of natural products, drugs, and polymers, and study of individual organic molecules in the laboratory and via theoretical (in silico) study. The range of chemicals studied chemistry includes hydrocarbons (compounds containing only carbon and hydrogen) as well as compounds based on carbon, but a ...
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Pericyclic Reaction
In organic chemistry, a pericyclic reaction is the type of organic reaction wherein the transition state of the molecule has a cyclic geometry, the reaction progresses in a concerted fashion, and the bond orbitals involved in the reaction overlap in a continuous cycle at the transition state. Pericyclic reactions stand in contrast to ''linear reactions'', encompassing most organic transformations and proceeding through an acyclic transition state, on the one hand and '' coarctate reactions'', which proceed through a doubly cyclic, concerted transition state on the other hand. Pericyclic reactions are usually rearrangement or addition reactions. The major classes of pericyclic reactions are given in the table below (the three most important classes are shown in bold). Ene reactions and cheletropic reactions are often classed as group transfer reactions and cycloadditions/cycloeliminations, respectively, while dyotropic reactions and group transfer reactions (if ene reactions ar ...
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Linear Topology
In algebra, a linear topology on a left A-module M is a topology on M that is invariant under translations and admits a fundamental system of neighborhoods of 0 that consist of submodules of M. If there is such a topology, M is said to be linearly topologized. If A is given a discrete topology, then M becomes a topological A-module with respect to a linear topology. The notion is used more commonly in algebra than in analysis. Indeed, " pological vector spaces with linear topology form a natural class of topological vector spaces ''over discrete fields'', analogous to the class of locally convex topological vector spaces over the normed fields of real or complex numbers in functional analysis Functional analysis is a branch of mathematical analysis, the core of which is formed by the study of vector spaces endowed with some kind of limit-related structure (for example, Inner product space#Definition, inner product, Norm (mathematics ...." The term "linear topology" goes bac ...
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