Aryl Radical
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Aryl Radical
An aryl radical in organic chemistry is a reactive intermediate and an arene compound incorporating one free radical carbon atom as part of the ring structure. As such it is the radical counterpart of the arenium ion. The parent compound is the phenyl radical .''Minireview Intermolecular Olefin Functionalisation Involving Aryl Radicals Generated from Arenediazonium Salts'' Markus R. Heinrich Chemistry - A European Journal 2008 volume 15 issue 4, pages 820 - 833 Aryl radicals are intermediates in certain organic reactions. Synthesis Aryl radicals can be obtained via aryl diazonium salts. Alternatives for these salts are certain aryl triazenes and aryl hydrazines. Aryl bromides and iodides can be converted to aryl radicals via tributyltin hydride and related compounds and silyl hydrides. Aryl halides can also be converted via electrochemical cathodic reduction The mushroom ''Stephanospora caroticolor'' is suspected to generate an aryl radical as part of its biological chemical defe ...
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Organic Chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and 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 and chemical properties, and evaluation of chemical reactivity to understand their behavior. The study of organic reactions includes the 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 in organic chemistry includes hydrocarbons (compounds containing only carbon and hydrogen) as well as compounds based on carbon, but also containing other elements, especially oxygen, nitrogen, sulfur, phosphorus (included in ...
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Electrosynthesis
Electrosynthesis in chemistry is the synthesis of chemical compounds in an electrochemical cell. Compared to ordinary redox reaction, electrosynthesis sometimes offers improved selectivity and yields. Electrosynthesis is actively studied as a science and also has industrial applications. Electrooxidation has potential for wastewater treatment as well. Experimental setup The basic setup in electrosynthesis is a galvanic cell, a potentiostat and two electrodes. Typical solvent and electrolyte combinations minimizes electrical resistance. Protic conditions often use alcohol-water or dioxane-water solvent mixtures with an electrolyte such as a soluble salt, acid or base. Aprotic conditions often use an organic solvent such as acetonitrile or dichloromethane with electrolytes such as lithium perchlorate or tetrabutylammonium salts. The choice of electrodes with respect to their composition and surface area can be decisive. For example, in aqueous conditions the competing reactions in th ...
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Iminium Ion
In organic chemistry, an iminium cation is a polyatomic ion with the general structure . They are common in synthetic chemistry and biology. Structure Iminium cations adopt alkene-like geometries. The central C=N unit is nearly coplanar with all four substituents. The C=N distances, which are near 129 picometers in length, are shorter than C-N single bonds. Cis/trans isomers are observed. Formation Iminium cations are obtained by protonation and alkylation of imines: :RN=CR'_2 + H+ -> [RNH=CR'_2]+ :RN=CR'_2 + R''+ -> [RR''N=CR'_2]+ They also are generated by the condensation of secondary amines with ketones or aldehydes: :O=CR'_2 + R2NH + H+ [R2N=CR'_2]+ + H2O This rapid, reversible reaction is one step in "iminium catalysis". More exotic routes to iminium cations are known, e.g. from ring-opening reactions of pyridine. Occurrence Iminium derivatives are common in biology. Pyridoxal phosphate reacts with amino acids to give iminium derivatives. Many iminium sal ...
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Sandmeyer Reaction
The Sandmeyer reaction is a chemical reaction used to synthesize aryl halides from aryl diazonium salts using copper salts as reagents or catalysts. It is an example of a radical-nucleophilic aromatic substitution. The Sandmeyer reaction provides a method through which one can perform unique transformations on benzene, such as halogenation, cyanation, trifluoromethylation, and hydroxylation. : The reaction was discovered in 1884 by Swiss chemist Traugott Sandmeyer, when he attempted to synthesize phenylacetylene from benzenediazonium chloride and copper(I) acetylide. Instead, the main product he isolated was chlorobenzene. In modern times, the Sandmeyer reaction refers to any method for substitution of an aromatic amino group via preparation of its diazonium salt followed by its displacement with a nucleophile in the presence of catalytic copper(I) salts. (Due to the low cost of copper salts, a stoichiometric amount is often employed for better reactivity even when catalysis is ...
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Coupling Reaction
A coupling reaction in organic chemistry is a general term for a variety of reactions where two fragments are joined together with the aid of a metal catalyst. In one important reaction type, a main group organometallic compound of the type R-M (R = organic fragment, M = main group center) reacts with an organic halide of the type R'-X with formation of a new carbon-carbon bond in the product R-R'. The most common type of coupling reaction is the cross coupling reaction. Richard F. Heck, Ei-ichi Negishi, and Akira Suzuki were awarded the 2010 Nobel Prize in Chemistry for developing palladium-catalyzed cross coupling reactions. Broadly speaking, two types of coupling reactions are recognized: *Heterocouplings combine two different partners, such as in the Heck reaction of an alkene (RC=CH) and an alkyl halide (R'-X) to give a substituted alkene, or the Corey–House synthesis of an alkane by the reaction of a lithium diorganylcuprate (R2CuLi) with an organyl (pseudo)halide (R'X ...
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Meerwein Arylation
The Meerwein arylation is an organic reaction involving the addition of an aryl diazonium salt (ArN2X) to an electron-poor alkene usually supported by a metal salt. The reaction product is an alkylated arene compound. The reaction is named after Hans Meerwein, one of its inventors who first published it in 1939. An electron-withdrawing group (EWG) on the alkene makes it electron deficient and although the reaction mechanism is unclear, involvement of an aryl radical is presumed after loss of nitrogen in the diazonium salt followed by a free radical addition. In the primary reaction product the intermediate alkyl radical is then captured by the diazonium counterion X which is usually a halogen or a tetrafluoroborate. In a subsequent step an elimination reaction liberates HX (for instance hydrochloric acid) and an aryl vinyl compound is formed. The reaction mechanism from the arene's view ranks as a radical-nucleophilic aromatic substitution. In a general scope a Meerwein ar ...
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Side Reaction
A side reaction is a chemical reaction that occurs at the same time as the actual main reaction, but to a lesser extent. It leads to the formation of by-product, so that the yield of main product is reduced: : + B ->[] P1 : + C ->[] P2 P1 is the main product if k1> k2. The by-product P2 is generally undesirable and must be Separation process, separated from the actual main product (usually in a Industrial separation processes, costly process). In organic synthesis B and C from the above equations usually represent different compounds. However, they could also just be different positions in the same molecule. A side reaction is also referred to as competing reaction when different compounds (B, C) compete for another reactant (A). If the side reaction occurs about as often as the main reaction, it is spoken of parallel reactions (especially in the kinetics, see below). Also there may be more complicated relationships: Compound A could reversibly but quickly react to substan ...
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UV Spectroscopy
Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nm (with a corresponding frequency around 30  PHz) to 400 nm (750  THz), shorter than that of visible light, but longer than X-rays. UV radiation is present in sunlight, and constitutes about 10% of the total electromagnetic radiation output from the Sun. It is also produced by electric arcs and specialized lights, such as mercury-vapor lamps, tanning lamps, and black lights. Although long-wavelength ultraviolet is not considered an ionizing radiation because its photons lack the energy to ionize atoms, it can cause chemical reactions and causes many substances to glow or fluoresce. Consequently, the chemical and biological effects of UV are greater than simple heating effects, and many practical applications of UV radiation derive from its interactions with organic molecules. Short-wave ultraviolet light damages DNA and sterilizes surfaces with which it comes into contact. For huma ...
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Electron Paramagnetic Resonance
Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials that have unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but the spins excited are those of the electrons instead of the atomic nuclei. EPR spectroscopy is particularly useful for studying metal complexes and organic radicals. EPR was first observed in Kazan State University by Soviet physicist Yevgeny Zavoisky in 1944, and was developed independently at the same time by Brebis Bleaney at the University of Oxford. Theory Origin of an EPR signal Every electron has a magnetic moment and spin quantum number s = \tfrac , with magnetic components m_\mathrm = + \tfrac or m_\mathrm = - \tfrac . In the presence of an external magnetic field with strength B_\mathrm , the electron's magnetic moment aligns itself either antiparallel ( m_\mathrm = - \tfrac ) or parallel ( m_\mathrm = + \tfrac ) to the fie ...
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Biological Chemical Defence
Biology is the scientific study of life. It is a natural science with a broad scope but has several unifying themes that tie it together as a single, coherent field. For instance, all organisms are made up of cells that process hereditary information encoded in genes, which can be transmitted to future generations. Another major theme is evolution, which explains the unity and diversity of life. Energy processing is also important to life as it allows organisms to move, grow, and reproduce. Finally, all organisms are able to regulate their own internal environments. Biologists are able to study life at multiple levels of organization, from the molecular biology of a cell to the anatomy and physiology of plants and animals, and evolution of populations.Based on definition from: Hence, there are multiple subdisciplines within biology, each defined by the nature of their research questions and the tools that they use. Like other scientists, biologists use the scientific metho ...
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Mushroom
A mushroom or toadstool is the fleshy, spore-bearing fruiting body of a fungus, typically produced above ground, on soil, or on its food source. ''Toadstool'' generally denotes one poisonous to humans. The standard for the name "mushroom" is the cultivated white button mushroom, ''Agaricus bisporus''; hence the word "mushroom" is most often applied to those fungi ( Basidiomycota, Agaricomycetes) that have a stem ( stipe), a cap ( pileus), and gills (lamellae, sing. lamella) on the underside of the cap. "Mushroom" also describes a variety of other gilled fungi, with or without stems, therefore the term is used to describe the fleshy fruiting bodies of some Ascomycota. These gills produce microscopic spores that help the fungus spread across the ground or its occupant surface. Forms deviating from the standard morphology usually have more specific names, such as "bolete", "puffball", "stinkhorn", and " morel", and gilled mushrooms themselves are often called "agarics" in refere ...
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Silyl Hydride
Hydrosilanes are tetravalent silicon compounds containing one or more Si-H bond. The parent hydrosilane is silane (SiH4). Commonly, hydrosilane refers to organosilicon derivatives. Examples include phenylsilane (PhSiH3) and triethoxysilane ((C2H5O)3SiH). Polymers and oligomers terminated with hydrosilanes are resins that are used to make useful materials like caulks. Synthesis Trichlorosilane is produced commercially by the reaction of hydrogen chloride with silicon: :Si + 3 HCl → HSiCl3 + H2 Many alkoxy hydrosilanes are generated by alcoholysis of trichlorosilane. One example is triethoxysilane: :HSiCl3 + 3EtOH → HSi(OEt)3 + 3 HCl Organohydrosilanes can be prepared by partial hydrosilation of silane itself: :SiH4 + 3 C2H4 → HSi(C2H5)3 In the laboratory, hydrosilanes classically are prepared by treating chlorosilanes with hydride reagents, such as lithium aluminium hydride: :4ClSi(C2H5)3 + LiAlH4 → 4HSi(C2H5)3 + LiAlCl4 Structure The silicon-to-hydrogen bond is longer t ...
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