Blaise Ketone Synthesis
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Blaise Ketone Synthesis
The Blaise ketone synthesis (named after Edmond Blaise) is the chemical reaction of acid chlorides with organozinc compounds to give ketones. The reaction was claimed to bring excellent yields by Blaise, however, investigators failed to obtain better than moderate yields (50%). Thus, the reaction is particularly ineffective in forming ketones from acyl chlorides. The reaction also works with organocuprates. Reviews have been written. Reaction Mechanism The mechanism is sampled from the proposed mechanism for organocadmium compounds, given that the mechanisms are identical to one another the proposed mechanism for the reaction is the same as the one for organocadmium compounds. After the oxygen forms a bond with the organozinc compound, R’ shifts to the carbonyl carbon, having chlorine act as a leaving group and removing the negative charge from zinc. The chlorine that left returns to form a bond with zinc, pushing the electrons back on to oxygen and thus forming the keto ...
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Chemical Reaction
A chemical reaction is a process that leads to the IUPAC nomenclature for organic transformations, chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the positions of electrons in the forming and breaking of chemical bonds between atoms, with no change to the Atomic nucleus, nuclei (no change to the elements present), and can often be described by a chemical equation. Nuclear chemistry is a sub-discipline of chemistry that involves the chemical reactions of unstable and radioactive Chemical element, elements where both electronic and nuclear changes can occur. The substance (or substances) initially involved in a chemical reaction are called reagent, reactants or reagents. Chemical reactions are usually characterized by a chemical change, and they yield one or more Product (chemistry), products, which usually have properties different from the reactants. Reactions often consist of a sequence o ...
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Blaise Reaction
The Blaise reaction is an organic reaction that forms a β-ketoester from the reaction of zinc metal with a α-bromoester and a nitrile. The reaction was first reported by Edmond Blaise (1872–1939) in 1901. The final intermediate is a metaloimine, which is then hydrolyzed to give the desired β-ketoester. Bulky aliphatic esters tend to give higher yields. Steven Hannick and Yoshito Kishi have developed an improved procedure. It has been noted that free hydroxyl groups can be tolerated in the course of this reaction, which is surprising for reactions of organometallic halides. Mechanism The mechanism of the Blaise reaction involves the formation of an organozinc complex with the bromine alpha to the ester carbonyl. This makes the alpha carbon nucleophilic, allowing it to attack the electrophilic carbon of the nitrile. The negative nitrile nitrogen resulting from this attack complexes with the zinc monobromide cation. The β-enamino ester (tautomer of the imine intermedia ...
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Addition Reactions
Addition (usually signified by the plus symbol ) is one of the four basic operations of arithmetic, the other three being subtraction, multiplication and division. The addition of two whole numbers results in the total amount or '' sum'' of those values combined. The example in the adjacent image shows a combination of three apples and two apples, making a total of five apples. This observation is equivalent to the mathematical expression (that is, "3 ''plus'' 2 is equal to 5"). Besides counting items, addition can also be defined and executed without referring to concrete objects, using abstractions called numbers instead, such as integers, real numbers and complex numbers. Addition belongs to arithmetic, a branch of mathematics. In algebra, another area of mathematics, addition can also be performed on abstract objects such as vectors, matrices, subspaces and subgroups. Addition has several important properties. It is commutative, meaning that the order of the operands d ...
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Chem
Chem may refer to: * Chemistry practical waali mam *Chemistry *Chemical * ''Chem'' (journal), a scientific journal published by Cell Press *Post apocalyptic slang for "drugs", medicinal or otherwise in the Fallout video game series. In Ancient Egyptian usage: * ''Khem'' (also spelt ''Chem''), the Egyptian word for "black" * Min (god), in the past erroneously named ''Khem'' CHEM may refer to : *A metabolic panel: for instance, CHEM-7, which is the basic metabolic panel *CHEM-DT CHEM-DT is the TVA owned-and-operated television station in Trois-Rivières, Quebec, Canada. It broadcasts a high-definition digital signal on VHF channel 8 from a transmitter on Rue Principale in Notre-Dame-du-Mont-Carmel. Owned by the Grou ..., a Canadian television channel See also * Chemo (other) * Kemi, a place in Finland {{disambig ...
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Bull
A bull is an intact (i.e., not castrated) adult male of the species ''Bos taurus'' (cattle). More muscular and aggressive than the females of the same species (i.e., cows), bulls have long been an important symbol in many religions, including for sacrifices. These animals play a significant role in beef ranching, dairy farming, and a variety of sporting and cultural activities, including bullfighting and bull riding. Due to their temperament, handling requires precautions. Nomenclature The female counterpart to a bull is a cow, while a male of the species that has been castrated is a ''steer'', '' ox'', or ''bullock'', although in North America, this last term refers to a young bull. Use of these terms varies considerably with area and dialect. Colloquially, people unfamiliar with cattle may refer to both castrated and intact animals as "bulls". A wild, young, unmarked bull is known as a ''micky'' in Australia.Sheena Coupe (ed.), ''Frontier Country, Vol. 1'' (Weldon R ...
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Negishi Coupling
The Negishi coupling is a widely employed transition metal catalyzed cross-coupling reaction. The reaction couples organic halides or triflates with organozinc compounds, forming carbon-carbon bonds (C-C) in the process. A palladium (0) species is generally utilized as the metal catalyst, though nickel is sometimes used. A variety of nickel catalysts in either Ni0 or NiII oxidation state can be employed in Negishi cross couplings such as Ni(PPh3)4, Ni(acac)2, Ni(COD)2 etc. : :* The leaving group X is usually chloride, bromide, or iodide, but triflate and acetyloxy groups are feasible as well. X = Cl usually leads to slow reactions. :* The organic residue R = alkenyl, aryl, allyl, alkynyl or propargyl. :* The halide X' in the organozinc compound can be chloride, bromine or iodine and the organic residue R' is alkenyl, aryl, allyl, alkyl, benzyl, homoallyl, and homopropargyl. :* The metal M in the catalyst is nickel or palladium :* The ligand L in the catalyst can be triphenylp ...
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Sulfuric Acid
Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formula . It is a colorless, odorless and viscous liquid that is miscible with water. Pure sulfuric acid does not exist naturally on Earth due to its strong affinity to water vapor; it is hygroscopic and readily absorbs water vapor from the air. Concentrated sulfuric acid is highly corrosive towards other materials, from rocks to metals, since it is an oxidant with powerful dehydrating properties. Phosphorus pentoxide is a notable exception in that it is not dehydrated by sulfuric acid, but to the contrary dehydrates sulfuric acid to sulfur trioxide. Upon addition of sulfuric acid to water, a considerable amount of heat is released; thus the reverse procedure of adding water to the acid should not be performed since the heat released may boi ...
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Acid Chloride
In organic chemistry, an acyl chloride (or acid chloride) is an organic compound with the functional group . Their formula is usually written , where R is a side chain. They are reactive derivatives of carboxylic acids (). A specific example of an acyl chloride is acetyl chloride, . Acyl chlorides are the most important subset of acyl halides. Nomenclature Where the acyl chloride moiety takes priority, acyl chlorides are named by taking the name of the parent carboxylic acid, and substituting ''-yl chloride'' for ''-ic acid''. Thus: : : When other functional groups take priority, acyl chlorides are considered prefixes — ''chlorocarbonyl-'': : Properties Lacking the ability to form hydrogen bonds, acyl chlorides have lower boiling and melting points than similar carboxylic acids. For example, acetic acid boils at 118 °C, whereas acetyl chloride boils at 51 °C. Like most carbonyl compounds, infrared spectroscopy reveals a band near 1750 cm−1. The simplest s ...
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Blaise Ketone Synthesis Proposed Mechanism
Blaise is a personal name (from Greek Βλασιος, the name of Saint Blaise) and a place name. It can refer to: People * Blaise (name), including lists of people with the given name or surname ''Blaise'' Places France * Blaise-sous-Arzillières, a village and commune in the Marne ''département'' of north-eastern France * Blaise, a former commune of the Ardennes ''département'', now part of Vouziers * Blaise, a former commune of the Haute-Marne ''département'', now part of Colombey-les-Deux-Églises * Blaise (Marne), a tributary of the Marne River, northeastern France * Blaise (Eure), a tributary of the Eure (river), northern France Switzerland * The Gate of Blaise, an ancient city gate in Basel United Kingdom * Blaise Castle, a stately home in what is now the city of Bristol, England * Blaise Hamlet, built about 1811 for retired employees of the owner of Blaise Castle * Blaise High School, Bristol, England Other uses * Blaise (software), a computer-assisted ...
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Organocadmium Compound
An organocadmium compound is an organometallic compound containing a carbon to cadmium chemical bond. Organocadmium chemistry describes physical properties, synthesis, reactions and use of these compounds. Cadmium shares group 12 with zinc and mercury and their corresponding chemistries have much in common. The synthetic utility of organocadmium compounds is limited. The simplest organocadmium compound is dimethylcadmium. It is a linear molecule with a C-Cd bond length of 213 pm. Organocadmium compounds are typically sensitive to air, light, and moisture. Synthesis Dimethylcadmium and diethylcadmium were reported in 1917 by Erich Krause. In general, they are prepared by transmetalation or by an exchange reaction between an alkylating agent and a cadmium salt. According to one procedure, diethylcadmium is produced the reaction of cadmium bromide with two equivalents of the Grignard reagent ethylmagnesium bromide in diethyl ether. Diethylcadmium is a colorless oil with melti ...
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