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Deoxygenation
Deoxygenation is a chemical reaction involving the removal of oxygen atoms from a molecule. The term also refers to the removal of molecular oxygen (O2) from gases and solvents, a step in air-free technique and gas purifiers. As applied to organic compounds, deoxygenation is a component of fuels production as well a type of reaction employed in organic synthesis, e.g. of pharmaceuticals. Deoxygenation of C-O bonds With replacement by H2 The main examples involving the replacement of an oxo group by two hydrogen atoms (A=O → AH2) are hydrogenolysis. Typical examples use metal catalysts and H2 as the reagent. Conditions are typically more forcing than hydrogenation. Stoichiometric reactions that effect deoxygenation include the Wolff–Kishner reduction for aryl ketones. The replacement of a hydroxyl group by hydrogen (A-OH → A-H) is the point of the Barton–McCombie deoxygenation and the Markó–Lam deoxygenation. Biomass valorization Deoxygenation is an impo ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Wolff–Kishner Reduction
The Wolff–Kishner reduction is a reaction used in organic chemistry to convert carbonyl functionalities into methylene groups. In the context of complex molecule synthesis, it is most frequently employed to remove a carbonyl group after it has served its synthetic purpose of activating an intermediate in a preceding step. As such, there is no obvious retron for this reaction. The reaction was reported by Nikolai Kischner in 1911 and Ludwig Wolff in 1912, In general, the reaction mechanism first involves the ''in situ'' generation of a hydrazone by condensation of hydrazine with the ketone or aldehyde substrate. Sometimes it is however advantageous to use a pre-formed hydrazone as substrate (see modifications). The rate determining step of the reaction is de-protonation of the hydrazone by an alkoxide base to form a diimide anion by a concerted, solvent mediated protonation/de-protonation step. Collapse of this alkyldiimide with loss of N2 leads to formation of an alkylanion whic ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Barton–McCombie Deoxygenation
The Barton–McCombie deoxygenation is an organic reaction in which a hydroxy functional group in an organic compound is replaced by a hydrogen to give an alkyl group. It is named after British chemists Sir Derek Harold Richard Barton and Stuart W. McCombie. This deoxygenation reaction is a radical substitution. In the related Barton decarboxylation the reactant is a carboxylic acid. Mechanism The reaction mechanism consists of a catalytic radical initiation step and a propagation step. The alcohol (1) is first converted into a reactive carbonothioyl intermediate such as a thionoester or xanthate 2. Heating of AIBN results in its homolytic cleavage, generating two 2-cyanoprop-2-yl radicals 9 which each abstract a proton from tributylstannane 3 to generate tributylstannyl radicals 4 and inactive 10. The tributyltin radical abstracts the xanthate group from 2 by attack of 4 at the sulfur atom with concurrent homolytic cleavage of the C-S π bond. This leaves a carbon cen ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Epoxide
In organic chemistry, an epoxide is a cyclic ether () with a three-atom ring. This ring approximates an equilateral triangle, which makes it strained, and hence highly reactive, more so than other ethers. They are produced on a large scale for many applications. In general, low molecular weight epoxides are colourless and nonpolar, and often volatile. Nomenclature A compound containing the epoxide functional group can be called an epoxy, epoxide, oxirane, and ethoxyline. Simple epoxides are often referred to as oxides. Thus, the epoxide of ethylene (C2H4) is ethylene oxide (C2H4O). Many compounds have trivial names; for instance, ethylene oxide is called "oxirane". Some names emphasize the presence of the epoxide functional group, as in the compound ''1,2-epoxyheptane'', which can also be called ''1,2-heptene oxide''. A polymer formed from epoxide precursors is called an ''epoxy'', but such materials do not contain epoxide groups (or contain only a few residual epoxy ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Sulfoxide
In organic chemistry, a sulfoxide, also called a sulphoxide, is an organosulfur compound containing a sulfinyl () functional group attached to two carbon atoms. It is a polar functional group. Sulfoxides are oxidized derivatives of sulfides. Examples of important sulfoxides are alliin, a precursor to the compound that gives freshly crushed garlic its aroma, and dimethyl sulfoxide (DMSO), a common solvent. Structure and bonding Sulfoxides feature relatively short S–O distances. In DMSO, the S–O distance is 1.531 Å. The sulfur center is pyramidal; the sum of the angles at sulfur is about 306°.. Sulfoxides are generally represented with the structural formula R−S(=O)−R', where R and R' are organic groups. The bond between the sulfur and oxygen atoms is intermediate of a dative bond and a polarized double bond. The double-bond resonance form implies 10 electrons around sulfur (10-S-3 in N-X-L notation). The double-bond character of the S−O bond may be accoun ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Phosphine Oxide
Phosphine oxides are phosphorus compounds with the formula OPX3. When X = alkyl or aryl, these are organophosphine oxides. Triphenylphosphine oxide is an example. An inorganic phosphine oxide is phosphoryl chloride (POCl3). Structure and bonding Tertiary phosphine oxides Tertiary phosphine oxides are the most commonly encountered phosphine oxides. With the formula R3PO, they are tetrahedral compounds. They are usually prepared by oxidation of tertiary phosphines. The P-O bond is short and polar. According to molecular orbital theory, the short P–O bond is attributed to the donation of the lone pair electrons from oxygen p-orbitals to the antibonding phosphorus-carbon bonds. The nature of the P–O bond was once hotly debated. Some discussions invoked a role for phosphorus-centered d-orbitals in bonding, but this analysis is not supported by computational analyses. In terms of simple Lewis structure, the bond is more accurately represented as a dative bond, as is currently us ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Markó–Lam Deoxygenation
The Markó–Lam deoxygenation is an organic chemistry reaction where the hydroxy functional group in an organic compound is replaced by a hydrogen atom to give an alkyl group. The Markó-Lam reaction is a variant of the Bouveault–Blanc reduction and an alternative to the classical Barton–McCombie deoxygenation The Barton–McCombie deoxygenation is an organic reaction in which a hydroxy functional group in an organic compound is replaced by a hydrogen to give an alkyl group. It is named after British chemists Sir Derek Harold Richard Barton and Stuart .... It is named for the Belgian chemists István Markó and Kevin Lam. The main features of the reaction are: *short reaction time (5 seconds to 5 minutes). *the use of a stable toluate derivative. *the use of SmI2/ HMPA system or electrolysis instead of the classical and difficult to remove tributyltin hydride. Mechanism A hydroxyl group is first derivitised into a stable and very often crystalline toluate derivativ ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Oxophilic
Oxophilicity is the tendency of certain chemical compounds to form oxides by hydrolysis or abstraction of an oxygen atom from another molecule, often from organic compounds. The term is often used to describe metal centers, commonly the early transition metals such as titanium, niobium, and tungsten. Oxophilicity is often stated to be related to the hardness of the element, within the HSAB theory ( hard and soft (Lewis) acids and bases), but it has been shown that oxophilicity depends more on the electronegativity and effective nuclear charge of the element than on its hardness. This explains why the early transition metals, whose electronegativities and effective nuclear charges are low, are very oxophilic. Many main group compounds are also oxophilic, such as derivatives of aluminium, silicon, and phosphorus(III). The handling of oxophilic compounds often requires air-free techniques. Examples Complexes of oxophilic metals typically are prone to hydrolysis. For example, the high ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Tungsten Hexachloride
Tungsten hexachloride is the chemical compound of tungsten and chlorine with the formula WCl6. This dark violet blue species exists as a volatile solid under standard conditions. It is an important starting reagent in the preparation of tungsten compounds. Other examples of charge-neutral hexachlorides are rhenium(VI) chloride and molybdenum(VI) chloride. The highly volatile tungsten hexafluoride is also known. As a d0 ion, W(VI) forms diamagnetic derivatives. The hexachloride is octahedral with equivalent W–Cl distances of 2.24–2.26 Å. Preparation Tungsten hexachloride can be prepared by chlorinating tungsten metal in a sealed tube at 600 °C: : W + 3 Cl2 → WCl6 Properties and Reactions Tungsten (VI) chloride is a blue-black solid at room temperature. At lower temperatures, it becomes wine-red in color. A red form of the compound can be made by rapidly condensing its vapor, which reverts to the blue-black form on gentle heating. It is readily hydrolyzed, even ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Salt-free Reduction
In chemistry, salt-free reduction describes methodology for reduction of metal halides by electron-rich trimethylsilyl reagents. Traditional reductions of metal halides are accomplished with alkali metals, a process that cogenerates alkali metal salts. Using the salt-free reduction, the reduction of metal halides is accompanied by formation of neutral organic compounds that can be easily removed from the inorganic or organometallic product. In addition to the reduction of metal halides, the reagents associated with this methodology are applicable to deoxygenation of organic substrates. A typical reducing agent is N,N'-bis(trimethylsilyl)-4,4'-bipyridinylidene. Related pyrazine- and cyclohexadiene-based reagents have been developed. They are red or orange THF-soluble solids. The bipyridine reagent is produced by reduction of 4,4'-bipyridine in the presence of trimethylsilyl chloride (Me = CH3): : A typical reduction reaction is the conversion of tungsten hexachloride Tungste ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Arkivoc
''Arkivoc'' (''Archive for Organic Chemistry'') is a peer-reviewed open access scientific journal covering all aspects of organic chemistry. It is published by the non-profit organization Arkat USA, which was established in 2000 through a personal donation from Alan R. Katritzky and Linde Katritzky. ''Arkivoc'' is the primary publication of Arkat USA. According to the ''Journal Citation Reports'', the journal has a 2014 impact factor The impact factor (IF) or journal impact factor (JIF) of an academic journal is a scientometric index calculated by Clarivate that reflects the yearly mean number of citations of articles published in the last two years in a given journal, as ... of 1.165, ranking it 37th out of 57 journals in the category "Chemistry, Organic". Abstracting and Indexing According to the Journal Citation Reports, the journal has a 2018 impact factor of 1.253. The journal is indexed in Web of Science: Science Citation Index Expanded. References External lin ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Sodium Iodide
Sodium iodide (chemical formula NaI) is an ionic compound formed from the chemical reaction of sodium metal and iodine. Under standard conditions, it is a white, water-soluble solid comprising a 1:1 mix of sodium cations (Na+) and iodide anions (I−) in a crystal lattice. It is used mainly as a nutritional supplement and in organic chemistry. It is produced industrially as the salt formed when acidic iodides react with sodium hydroxide. It is a chaotropic salt. Uses Food supplement Sodium iodide, as well as potassium iodide, is commonly used to treat and prevent iodine deficiency. Iodized table salt contains 10 ppm iodide. Organic synthesis Sodium iodide is used for conversion of alkyl chlorides into alkyl iodides. This method, the Finkelstein reaction, relies on the insolubility of sodium chloride in acetone to drive the reaction: ::R–Cl + NaI → R–I + NaCl Nuclear medicine Some radioactive iodide salts of sodium, including Na 125I and Na 131I, have radio ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Trifluoroacetic Anhydride
Trifluoroacetic anhydride (TFAA) is the acid anhydride of trifluoroacetic acid. It is the perfluorinated derivative of acetic anhydride. Preparation Trifluoroacetic anhydride was originally prepared by the dehydration of trifluoroacetic acid with phosphorus pentoxide. The dehydration might also be carried out with excess α-halogenated acid chlorides. For example, with dichloroacetyl chloride: : 2 CF3COOH + Cl2CHCOCl → (CF3CO)2O + Cl2CHCOOH + HCl Uses Trifluoroacetic anhydride has various uses in organic synthesis. It may be used to introduce the corresponding trifluoroacetyl group, for which it is more convenient than the corresponding acyl chloride, trifluoroacetyl chloride, which is a gas. It can be used to promote reactions of carboxylic acids, including nucleophilic acyl substitution, Friedel-Crafts acylation, and acylation of other unsaturated compounds. Other electrophilic aromatic substitution reactions can also be promoted with trifluoroacetic anhydride, includi ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
