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Jordan-Ullmann-Goldberg Synthesis
The Ullmann condensation or Ullmann-type reaction is the copper-promoted conversion of aryl halides to aryl ethers, aryl thioethers, aryl nitriles, and aryl amines. These reactions are examples of cross-coupling reactions. Ullmann-type reactions are comparable to Buchwald–Hartwig reactions but usually require higher temperatures. Traditionally these reaction requires high-boiling polar solvents such as ''N''-methylpyrrolidone, nitrobenzene, or dimethylformamide and high temperatures (often in excess of 210 °C) with stoichiometric amounts of copper. Aryl halide were required to be activated by electron-withdrawing groups. Traditional Ullmann style reactions used "activated" copper powder, e.g. prepared in situ by the reduction of copper sulfate by zinc metal in hot water. The methodology improved with the introduction of soluble copper catalysts supported by diamines and acetylacetonate ligands. Ullmann ether synthesis: C-O coupling Illustrative of the traditional Ullma ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Fritz Ullmann
Fritz Ullmann (July 2, 1875 in Fürth – March 17, 1939 in Berlin) was a German chemist. Ullmann was born in Fürth and started studying chemistry in Nuremberg, but received his PhD of the University of Geneva for work with Carl Gräbe in 1895. After some time in Geneva he went to Berlin in 1905. Ullmann taught technical chemistry during 1905-1913 and 1922-1925 at the ''Technischen Hochschule Berlin'' now ''Technische Universität Berlin'', first as part of the ordinary teaching staff, later on as a professor. In 1900 he introduced dimethyl sulfate as an alkylating agent. Between 1914 and 1922, when he was back in Geneva, he published the first edition of the "Enzyklopädie der Technischen Chemie" in 12 volumes () in English the ''Ullmann's Encyclopedia of Industrial Chemistry'', a publication that exists to this day. He was married to Irma Goldberg who was his assistant from 1905 to 1910 at his laboratory. They named after themselves the following reactions: the Ullmann rea ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Phenanthroline
1,10-Phenanthroline (phen) is a heterocyclic organic compound. It is a white solid that is soluble in organic solvents. The 1,10 refer to the location of the nitrogen atoms that replace CH's in the hydrocarbon called phenanthrene. Abbreviated "phen", it is used as a ligand in coordination chemistry, forming strong complexes with most metal ions.Luman, C.R. and Castellano, F.N. (2003) "Phenanthroline Ligands" in Comprehensive Coordination Chemistry II. Elsevier. . It is often sold as the monohydrate. Synthesis Phenanthroline may be prepared by two successive Skraup reactions of glycerol with ''o''-phenylenediamine, catalyzed by sulfuric acid, and an oxidizing agent, traditionally aqueous arsenic acid or nitrobenzene. Dehydration of glycerol gives acrolein which condenses with the amine followed by a cyclization. Coordination chemistry In terms of its coordination properties, phenanthroline is similar to 2,2'-bipyridine (bipy) with the advantage that the two nitrogen donors ar ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Irma Goldberg
Irma Goldberg (born 1871) was one of the first female organic chemists to have and sustain a successful career, her work even being quoted in her own name in standard textbooks. Life Education Born in Moscow to a Russian-Jewish family, she later traveled to Geneva in the 1890s to study chemistry at Geneva University. Early research, Ullmann reaction Her early research included the development of a process to remove sulfur and phosphorus from acetylene. Her first article on the derivatives of benzophenone, coauthored by German chemist Fritz Ullmann, was published in 1897. She also researched and wrote a paper (published in 1904) on using copper as a catalyst for the preparation of a phenyl derivative of thiosalicylic acid, a process known as the Ullmann reaction; Goldberg is the only woman scientist unambiguously recognized for her own named reaction: the amidation (Goldberg) reaction. This modification to previous forms of the method was a great improvement, and was extremely ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Berichte Der Deutschen Chemischen Gesellschaft
''Chemische Berichte'' (usually abbreviated as ''Ber.'' or ''Chem. Ber.'') was a German-language scientific journal of all disciplines of chemistry founded in 1868. It was one of the oldest scientific journals in chemistry, until it merged with ''Recueil des Travaux Chimiques des Pays-Bas'' to form ''Chemische Berichte/Recueil'' in 1997. ''Chemische Berichte/Recueil'' was then merged with other European journals in 1998 to form ''European Journal of Inorganic Chemistry''. History Founded in 1868 as ''Berichte der Deutschen Chemischen Gesellschaft'' (, CODEN BDCGAS), it operated under this title until 1928 (Vol. 61). The journal was then split into: * ''Berichte der Deutschen Chemischen Gesellschaft, A: Vereins-Nachrichten'' (, CODEN BDCAAS), and * ''Berichte der Deutschen Chemischen Gesellschaft, B: Abhandlungen'' (, CODEN BDCBAD). Vol. 78 and 79 (1945–1946) were omitted and not published due to World War II. The journal was renamed ''Chemische Berichte'' (, CODEN CHBEAM) in 19 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Spectator Ligand
In coordination chemistry, a spectator ligand is a ligand that does not participate in chemical reactions of the complex. Instead, spectator ligands (vs "actor ligands") occupy coordination sites. Spectator ligands tend to be of polydentate, such that the M-spectator ensemble is inert kinetically. Although they do not participate in reactions of the metal, spectator ligands influence the reactivity of the metal center to which they are bound. These ligands are sometimes referred to as ancillary ligands. Several different classes of ligand exist that can be considered spectator ligands. A few examples include trispyrazolylborates (Tp), cyclopentadienyl ligands (Cp), and many chelating diphosphines such as 1,2-bis(diphenylphosphino)ethane 1,2-Bis(diphenylphosphino)ethane (dppe) is an organophosphorus compound with the formula (PhPCH) (Ph = phenyl). It is a commonly used bidentate ligand in coordination chemistry. It is a white solid that is soluble in organic solvents. Prepa ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 both in ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Malonic Ester
Diethyl malonate, also known as DEM, is the diethyl ester of malonic acid. It occurs naturally in grapes and strawberries as a colourless liquid with an apple-like odour, and is used in perfumes. It is also used to synthesize other compounds such as barbiturates, artificial flavourings, vitamin B1, and vitamin B6. Structure and properties Malonic acid is a rather simple dicarboxylic acid, with two the carboxyl groups close together. In forming diethyl malonate from malonic acid, the hydroxyl group (−OH) on both of the carboxyl groups is replaced by an ethoxy group (−OEt; −OCH2CH3). The methylene group (−CH2−) in the middle of the malonic part of the diethyl malonate molecule is neighboured by two carbonyl groups (−C(=O)−). The hydrogen atoms on the carbon adjacent to the carbonyl group in a molecule is significantly more acidic than hydrogen atoms on a carbon adjacent to alkyl groups (up to 30 orders of magnitude). (This is known as the α position with res ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Cyanide
Cyanide is a naturally occurring, rapidly acting, toxic chemical that can exist in many different forms. In chemistry, a cyanide () is a chemical compound that contains a functional group. This group, known as the cyano group, consists of a carbon atom triple-bonded to a nitrogen atom. In inorganic cyanides, the cyanide group is present as the anion . Soluble salts such as sodium cyanide (NaCN) and potassium cyanide (KCN) are highly toxic. Hydrocyanic acid, also known as hydrogen cyanide, or HCN, is a highly volatile liquid that is produced on a large scale industrially. It is obtained by acidification of cyanide salts. Organic cyanides are usually called nitriles. In nitriles, the group is linked by a covalent bond to carbon. For example, in acetonitrile (), the cyanide group is bonded to methyl (). Although nitriles generally do not release cyanide ions, the cyanohydrins do and are thus rather toxic. Bonding The cyanide ion is isoelectronic with carbon monoxide a ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Carbanion
In organic chemistry, a carbanion is an anion in which carbon is trivalent (forms three bonds) and bears a formal negative charge (in at least one significant resonance form). Formally, a carbanion is the conjugate base of a carbon acid: :R3CH\, + \ddot^- -> \mathbf + HB where B stands for the base. The carbanions formed from deprotonation of alkanes (at an sp3 carbon), alkenes (at an sp2 carbon), arenes (at an sp2 carbon), and alkynes (at an sp carbon) are known as alkyl, alkenyl (vinyl), aryl, and alkynyl (acetylide) anions, respectively. Carbanions have a concentration of electron density at the negatively charged carbon, which, in most cases, reacts efficiently with a variety of electrophiles of varying strengths, including carbonyl groups, imines/ iminium salts, halogenating reagents (e.g., ''N''-bromosuccinimide and diiodine), and proton donors. A carbanion is one of several reactive intermediates in organic chemistry. In organic synthesis, organolithium reagents a ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Journal Of Organic Chemistry
''The Journal of Organic Chemistry'', colloquially known as ''JOC'', is a peer-reviewed scientific journal for original contributions of fundamental research in all branches of theory and practice in organic and bioorganic chemistry. It is published by the publishing arm of the American Chemical Society, with 24 issues per year. According to the ''Journal Citation Reports'', the journal had a 2017 impact factor of 4.805 and it is the journal that received the most cites (100,091 in 2017) in the field of organic chemistry. According to Web of Knowledge (and as December 2012), eleven papers from the journal have received more than 1,000 citations, with the most cited paper having received 7,967 citations. The current editor-in-chief is Scott J. Miller from Yale University. Indexing ''J. Org. Chem.'' is currently indexed in: See also *Organic Letters *Organometallics ''Organometallics'' is a biweekly journal published by the American Chemical Society. Its area of focus is ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
