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Reductive Dehalogenation Of Halo Ketones
In organic chemistry, α-halo ketones can be reduced with loss of the halogen atom to form enolates. The α-halo ketones are readily prepared from ketones by various ketone halogenation reactions, and the products are reactive intermediates that can be used for a variety of other chemical reactions. Introduction The reduction of α-halo ketones generates a variety of product structures that may exhibit unique substitution patterns and reactivity. For instance, reduction of α,α'-dihalo ketones leads to 2-oxyallyl metal complexes, which participate in +3and +2cycloaddition reactions as the 2π component.Rigby, J.; Pigge, C. ''Org. React.'' 1997, ''51'', 351. 2-Oxyallyl metal intermediates may also intercept nucleophiles in a process that involves umpolung at the α carbon. In addition, because reduction of monohalo ketones produces enolates in a site-specific fashion, reactions associated with enolates (alkylation, aldol, Michael) may be carried out using halo ketone substrates ...
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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 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 in organic chemistry includes hydrocarbons (compounds containing only carbon and hydrogen) as well as compounds based on carbon, but also con ...
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Transition Metal Complex
A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many metal-containing compounds, especially those that include transition metals (elements like titanium that belong to the Periodic Table's d-block), are coordination complexes. Nomenclature and terminology Coordination complexes are so pervasive that their structures and reactions are described in many ways, sometimes confusingly. The atom within a ligand that is bonded to the central metal atom or ion is called the donor atom. In a typical complex, a metal ion is bonded to several donor atoms, which can be the same or different. A polydentate (multiple bonded) ligand is a molecule or ion that bonds to the central atom through several of the ligand's atoms; ligands with 2, 3, 4 or even 6 bonds to the central atom are common. These compl ...
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Cyclopropanone
Cyclopropanone is an organic compound with molecular formula (CH2)2CO consisting of a cyclopropane carbon framework with a ketone functional group. The parent compound is labile, being highly sensitive toward even weak nucleophiles. Surrogates of cyclopropanone include the ketals. Preparation Cyclopropanone has been prepared by reaction of ketene with diazomethane. These solutions are stable at −78 °C. In the presence of protic reagents such as carboxylic acids, primary and secondary amines, and alcohols, cyclopropanone converts to adducts, which are often isolatable at room temperature: :(CH2)2CO + X-H → (CH2)2C(X)(OH) (X-H = R2N-H, HO-H, RO-H) Structure and bonding The C3O atoms are coplanar. As deduced from the microwave spectrum, the H2C-CH2 bond length of 157.5 pm is unusually long. By contrast, the C-C bond lengths in cyclopropane are 151 pm. The C=O bond length of 119 pm is short compared to the 123 pm bond length in acetone. The value of νC=O in the ...
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Diene
In organic chemistry a diene ( ) (diolefin ( ) or alkadiene) is a covalent compound that contains two double bonds, usually among carbon atoms. They thus contain two alk''ene'' units, with the standard prefix ''di'' of systematic nomenclature. As a subunit of more complex molecules, dienes occur in naturally occurring and synthetic chemicals and are used in organic synthesis. Conjugated dienes are widely used as monomers in the polymer industry. Polyunsaturated fats are of interest to nutrition. Classes Dienes can be divided into three classes, depending on the relative location of the double bonds: #Cumulated dienes have the double bonds sharing a common atom. The result is more specifically called an allene. #Conjugated dienes have conjugated double bonds separated by one single bond. Conjugated dienes are more stable than other dienes because of resonance. #Unconjugated dienes have the double bonds separated by two or more single bonds. They are usually less stable than ...
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Protic Solvent
In chemistry, a protic solvent is a solvent that has a hydrogen atom bound to an oxygen (as in a hydroxyl group ), a nitrogen (as in an amine group or ), or fluoride (as in hydrogen fluoride). In general terms, any solvent that contains a labile is called a protic solvent. The molecules of such solvents readily donate protons () to solutes, often via hydrogen bonding In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing .... Water is the most common protic solvent. Conversely, polar aprotic solvents cannot donate protons but still have the ability to dissolve many salts. Methods for purification of common solvents are available See also * Autoprotolysis References {{Chemical solutions Solvents ...
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Geminal
In chemistry, the descriptor geminal () refers to the relationship between two atoms or functional groups that are attached to the same atom. A geminal diol, for example, is a diol (a molecule that has two alcohol functional groups) attached to the same carbon atom, as in methanediol. Also the shortened prefix ''gem'' may be applied to a chemical name to denote this relationship, as in a ''gem''-dibromide for "geminal dibromide". The concept is important in many branches of chemistry, including synthesis and spectroscopy, because functional groups attached to the same atom often behave differently from when they are separated. Geminal diols, for example, are easily converted to ketones or aldehydes with loss of water.Peter Taylor (2002)''Mechanism and synthesis'' Book 10 of ''Molecular world''. Open University, Royal Society of Chemistry; . 368 pages The related term vicinal refers to the relationship between two functional groups that are attached to adjacent atoms. The ...
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Disproportionation
In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. More generally, the term can be applied to any desymmetrizing reaction of the following type, regardless of whether it is a redox or some other type of process: :2A -> A' + A'' Examples * Mercury(I) chloride disproportionates upon UV-irradiation: :Hg2Cl2 → Hg + HgCl2 * Phosphorous acid disproportionates upon heating to give phosphoric acid and phosphine: :4 → 3 H3PO4 + PH3 *Desymmetrizing reactions are sometimes referred to as disproportionation, as illustrated by the thermal degradation of bicarbonate: :2 → + H2CO3 :The oxidation numbers remain constant in this acid-base reaction. This process is also called autoionization. *Another variant on disproportionation is radical disproportionation, in which two radicals form an alkene and an alkane. : R ...
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Oxidative Addition
Oxidative addition and reductive elimination are two important and related classes of reactions in organometallic chemistry. Oxidative addition is a process that increases both the oxidation state and coordination number of a metal centre. Oxidative addition is often a step in catalytic cycles, in conjunction with its reverse reaction, reductive elimination. Role in transition metal chemistry For transition metals, oxidative reaction results in the decrease in the d''n'' to a configuration with fewer electrons, often 2e fewer. Oxidative addition is favored for metals that are (i) basic and/or (ii) easily oxidized. Metals with a relatively low oxidation state often satisfy one of these requirements, but even high oxidation state metals undergo oxidative addition, as illustrated by the oxidation of Pt(II) with chlorine: : tCl4sup>2− + Cl2 → tCl6sup>2− In classical organometallic chemistry, the formal oxidation state of the metal and the electron count of the complex bot ...
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Zinc
Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic table. In some respects, zinc is chemically similar to magnesium: both elements exhibit only one normal oxidation state (+2), and the Zn2+ and Mg2+ ions are of similar size.The elements are from different metal groups. See periodic table. Zinc is the 24th most abundant element in Earth's crust and has five stable isotopes. The most common zinc ore is sphalerite (zinc blende), a zinc sulfide mineral. The largest workable lodes are in Australia, Asia, and the United States. Zinc is refined by froth flotation of the ore, roasting, and final extraction using electricity ( electrowinning). Zinc is an essential trace element for humans, animals, plants and for microorganisms and is necessary for prenatal and postnatal development. It ...
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