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Lithium Bis(trimethylsilyl)amide
Lithium bis(trimethylsilyl)amide is a lithiated organosilicon compound with the formula . It is commonly abbreviated as LiHMDS or Li(HMDS) (lithium hexamethyldisilazide - a reference to its conjugate acid HMDS) and is primarily used as a strong non-nucleophilic base and as a ligand. Like many lithium reagents, it has a tendency to aggregate and will form a cyclic trimer in the absence of coordinating species. Preparation LiHMDS is commercially available, but it can also be prepared by the deprotonation of bis(trimethylsilyl)amine with ''n''-butyllithium. This reaction can be performed ''in situ''. : Once formed, the compound can be purified by sublimation or distillation. Reactions and applications As a base LiHMDS is often used in organic chemistry as a strong non-nucleophilic base. Its conjugate acid has a p''K''a of ~26, making it is less basic than other lithium bases, such as LDA (p''K''a of conjugate acid ~36). It is relatively more sterically hindered and h ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Hexane
Hexane () or ''n''-hexane is an organic compound, a straight-chain alkane with six carbon atoms and the molecular formula C6H14. Hexane is a colorless liquid, odorless when pure, and with a boiling point of approximately . It is widely used as a cheap, relatively safe, largely unreactive, and easily evaporated non-polar solvent, and modern gasoline blends contain about 3% hexane. The term hexanes refers to a mixture, composed largely (>60%) of ''n''-hexane, with varying amounts of the isomeric compounds 2-methylpentane and 3-methylpentane, and possibly, smaller amounts of nonisomeric C5, C6, and C7 (cyclo)alkanes. These "hexanes" mixtures are cheaper than pure hexane and are often used in large-scale operations not requiring a single isomer (e.g., as cleaning solvent or for chromatography). Isomers Uses In industry, hexanes are used in the formulation of adhesive, glues for shoes, leather products, and roofing. They are also used to extract cooking oils (such as canola oil ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Acid Dissociation Constant
In chemistry, an acid dissociation constant (also known as acidity constant, or acid-ionization constant; denoted ) is a quantitative property, quantitative measure of the acid strength, strength of an acid in Solution (chemistry), solution. It is the equilibrium constant for a chemical reaction :HA A^- + H^+ known as Dissociation (chemistry), dissociation in the context of acid–base reactions. The chemical species HA is an acid that dissociates into , called the conjugate base of the acid, and a hydron (chemistry), hydrogen ion, . The system is said to be in chemical equilibrium, equilibrium when the concentrations of its components do not change over time, because both forward and backward reactions are occurring at the same rate. The dissociation constant is defined by :K_\text = \mathrm, or by its logarithmic form :\mathrmK_\ce = - \log_ K_\text = \log_\frac where quantities in square brackets represent the molar concentrations of the species at equilibrium. For example ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Trimethylsilyl Chloride
Trimethylsilyl chloride, also known as chlorotrimethylsilane is an organosilicon compound ( silyl halide), with the formula , often abbreviated or TMSCl. It is a colourless volatile liquid that is stable in the absence of water. It is widely used in organic chemistry. Preparation TMSCl is prepared on a large scale by the '' direct process'', the reaction of methyl chloride with a silicon-copper alloy. The principal target of this process is dimethyldichlorosilane, but substantial amounts of the trimethyl and monomethyl products are also obtained. The relevant reactions are (Me = methyl, ): x\ \ce \longrightarrow \begin \ce, \\ pt \ce, \\ pt \ce,\\ pt \text \end Typically about 2–4% of the product stream is the monochloride, which forms an azeotrope with . Reactions and uses TMSCl is reactive toward nucleophiles, resulting in the replacement of the chloride. In a characteristic reaction of TMSCl, the nucleophile is water, resulting in hydrolysis to give the hexa ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Sulfuryl Chloride
Sulfuryl chloride is an inorganic compound with the formula SO2Cl2. At room temperature, it is a colorless liquid with a pungent odor. Sulfuryl chloride is not found in nature. Sulfuryl chloride is commonly confused with thionyl chloride, SOCl2. The properties of these two sulfur oxychlorides are quite different: sulfuryl chloride is a source of chlorine whereas thionyl chloride is a source of chloride ions. An alternative IUPAC name is sulfuryl dichloride. Sulfur is tetrahedral in SO2Cl2 and the oxidation state of the sulfur atom is +6, as in sulfuric acid. Synthesis SO2Cl2 is prepared by the reaction of sulfur dioxide and chlorine in the presence of a catalyst, such as activated carbon. :SO2 + Cl2 → SO2Cl2 The product can be purified by fractional distillation. Legacy routes Sulfuryl chloride was first prepared in 1838 by the French chemist Henri Victor Regnault. Older routes include oxidation of thionyl chloride: :5 SOCl2 + HgO → ClSSCl + HgCl2 + 3 SO2Cl2 :2 SOCl2 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Sulfur Dichloride
Sulfur dichloride is the chemical compound with the formula . This cherry-red liquid is the simplest sulfur chloride and one of the most common, and it is used as a precursor to organosulfur compounds. It is a highly corrosive and toxic substance, and it reacts on contact with water to form chlorine-containing acids. Chlorination of sulfur is produced by the chlorination of either elemental sulfur or disulfur dichloride. The process occurs in a series of steps, some of which are: :; ''ΔH'' = −58.2 kJ/mol :; ''ΔH'' = −40.6 kJ/mol The addition of to has been proposed to proceed via a mixed valence intermediate . undergoes even further chlorination to give , but this species is unstable at near room temperature. It is likely that several exist where ''n'' > 2. Disulfur dichloride, , is a common impurity in . Separation of from is possible via distillation with to form an azeotrope of 99% purity. Sulfur dichloride loses chlorine slowly at room temperature, convert ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Tetrasulfur Tetranitride
Tetrasulfur tetranitride is an inorganic compound with the formula . This vivid orange, opaque, crystalline explosive is the most important binary sulfur nitride, which are compounds that contain only the elements sulfur and nitrogen. It is a precursor to many S-N compounds and has attracted wide interest for its unusual structure and bonding. Nitrogen and sulfur have similar electronegativities. When the properties of atoms are so highly similar, they often form extensive families of covalently bonded structures and compounds. Indeed, a large number of S-N and S-NH compounds are known with as their parent. Structure adopts an unusual "extreme cradle" structure, with D2d point group symmetry. It can be viewed as a derivative of a (hypothetical) eight-membered ring (or more simply a 'deformed' eight-membered ring) of alternating sulfur and nitrogen atoms. The pairs of sulfur atoms across the ring are separated by 2.586 Å, resulting in a cage-like structure as determine ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Claisen Condensation
The Claisen condensation is a carbon–carbon bond forming reaction that occurs between two esters or one ester and another carbonyl compound in the presence of a strong base. The reaction produces a β-keto ester or a β- diketone. It is named after Rainer Ludwig Claisen, who first published his work on the reaction in 1887. The reaction has often been displaced by diketene-based chemistry, which affords acetoacetic esters. Requirements At least one of the reagents must be enolizable (have an α-proton and be able to undergo deprotonation to form the enolate anion). There are a number of different combinations of enolizable and nonenolizable carbonyl compounds that form a few different types of Claisen. The base used must not interfere with the reaction by undergoing nucleophilic substitution or addition with a carbonyl carbon. For this reason, the conjugate sodium alkoxide base of the alcohol formed (e.g. sodium ethoxide if ethanol is formed) is often used, since the a ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Fráter–Seebach Alkylation
In organic chemistry, the Fráter–Seebach alkylation (also known as Seebach–Fráter alkylation or Fráter–Seebach reaction) is a diastereoselective alkylation of chiral beta-hydroxy esters using strong base (chemistry), bases. The reaction was first published by Georg Fráter in 1979; in 1980, Dieter Seebach reported about a similar reaction with malic acid ester. Outline and mechanism Chiral beta-hydroxy esters can be treated with two equivalents of a strong base (lithium diisopropylamide, lithium diisopropylamide (LDA) or Lithium bis(trimethylsilyl)amide, lithium bis(trimethylsilyl)amide (LHMDS) are popular choices) to both remove the proton on the alcohol and Enolization, enolize the ester. An alkylating agent (methyl iodide in the case of Fráter's publication) is then added. This attacks from the opposite face of the chiral hydroxyl group to avoid steric hindrance as shown below in the 6-membered transition state with Chelation, chelating metal ions. This reaction has ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
LiHMDS EnolateFormation
Lithium bis(trimethylsilyl)amide is a lithiated organosilicon compound with the formula . It is commonly abbreviated as LiHMDS or Li(HMDS) (lithium hexamethyldisilazide - a reference to its conjugate acid HMDS) and is primarily used as a strong non-nucleophilic base and as a ligand. Like many lithium reagents, it has a tendency to aggregate and will form a cyclic trimer in the absence of coordinating species. Preparation LiHMDS is commercially available, but it can also be prepared by the deprotonation of bis(trimethylsilyl)amine with ''n''-butyllithium. This reaction can be performed ''in situ''. : Once formed, the compound can be purified by sublimation or distillation. Reactions and applications As a base LiHMDS is often used in organic chemistry as a strong non-nucleophilic base. Its conjugate acid has a p''K''a of ~26, making it is less basic than other lithium bases, such as LDA (p''K''a of conjugate acid ~36). It is relatively more sterically hindered and he ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Enolate
In organic chemistry, enolates are organic anions derived from the deprotonation of carbonyl () compounds. Rarely isolated, they are widely used as reagents in the Organic synthesis, synthesis of organic compounds. Bonding and structure Enolate anions are electronically related to allyl anions. The anionic charge is delocalized over the oxygen and the two carbon sites. Thus they have the character of both an alkoxide and a carbanion. Although they are often drawn as being simple salts, in fact they adopt complicated structures often featuring aggregates. Preparation Deprotonation of enolizable ketones, aromatic alcohols, aldehydes, and esters gives enolates. With strong bases, the deprotonation is quantitative. Typically enolates are generated from using lithium diisopropylamide (LDA). Often, as in conventional Claisen condensations, Mannich reactions, and aldol condensations, enolates are generated in low concentrations with alkoxide bases. Under such conditions, they ex ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Acetylide
In chemistry, an acetylide is a compound that can be viewed as the result of replacing one or both hydrogen atoms of acetylene (ethyne) by metallic or other cations. Calcium carbide is an important industrial compound, which has long been used to produce acetylene for welding and illumination. It is also a major precursor to vinyl chloride. Other acetylides are reagents in organic synthesis. Nomenclature The term acetylide is used loosely. It apply to an acetylene , where R = H or a side chain that is usually organic. The nomenclature can be ambiguous with regards to the distinction between compounds of the type and . When both hydrogens of acetylene are replaced by metals, the compound can also be called carbide, e.g. calcium carbide , which is calcium acetylide. When only one hydrogen atom is replaced, the anion may be called hydrogen acetylide or the prefix ''mono''- may be attached to the metal, as in monosodium acetylide or sodium hydrogen acetylide, . An acetylide may b ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organolithium
In organometallic chemistry, organolithium reagents are chemical compounds that contain carbon–lithium (C–Li) bonds. These reagents are important in organic synthesis, and are frequently used to transfer the organic group or the lithium atom to the substrates in synthetic steps, through nucleophilic addition or simple deprotonation. Organolithium reagents are used in industry as an initiator for anionic polymerization, which leads to the production of various elastomers. They have also been applied in asymmetric synthesis in the pharmaceutical industry. Due to the large difference in electronegativity between the carbon atom and the lithium atom, the C−Li bond is highly ionic. Owing to the polar nature of the C−Li bond, organolithium reagents are good nucleophiles and strong bases. For laboratory organic synthesis, many organolithium reagents are commercially available in solution form. These reagents are highly reactive, and are sometimes pyrophoric. History and de ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
