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Barton Decarboxylation
The Barton decarboxylation is a radical reaction in which a carboxylic acid is converted to a thiohydroxamate ester (commonly referred to as a Barton ester). The product is then heated in the presence of a radical initiator and a suitable hydrogen donor to afford the decarboxylated product. This is an example of a reductive decarboxylation. Using this reaction it is possible to remove carboxylic acid moieties from alkyl groups and replace them with other functional groups. (See Scheme 1) This reaction is named after its developer, the British chemist and Nobel laureate Sir Derek Barton (1918–1998). : Mechanism The reaction is initiated by homolytic cleavage of a radical initiator, in this case 2,2'-azobisisobutyronitrile ( AIBN), upon heating. A hydrogen is then abstracted from the hydrogen source ( tributylstannane in this case) to leave a tributylstannyl radical that attacks the sulfur atom of the thiohydroxamate ester. The N-O bond of the thiohydroxamate ester undergoes ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Derek Barton
Sir Derek Harold Richard Barton (8 September 1918 – 16 March 1998) was an English organic chemist and Nobel Prize laureate for 1969. Education and early life Barton was born in Gravesend, Kent, to William Thomas and Maude Henrietta Barton (''née'' Lukes). He attended Gravesend Grammar School (1926–29), The King's School, Rochester (1929–32), Tonbridge School (1932–35) and Medway Technical College (1937–39). In 1938 he entered Imperial College London, where he graduated in 1940 and obtained his PhD degree in Organic Chemistry in 1942. Career and research From 1942 to 1944 Barton was a government research chemist, then from 1944 to 1945 he worked for Albright and Wilson in Birmingham. He then became Assistant Lecturer in the Department of Chemistry of Imperial College, and from 1946 to 1949 he was ICI Research Fellow. During 1949 and 1950 he was visiting lecturer in natural products chemistry at Harvard University, and was then appointed reader in organic chemistr ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Homolysis (chemistry)
In chemistry, homolysis () or homolytic fission is the dissociation of a molecular bond by a process where each of the fragments (an atom or molecule) retains one of the originally bonded electrons. During homolytic fission of a neutral molecule with an even number of electrons, two free radicals will be generated. That is, the two electrons involved in the original bond are distributed between the two fragment species. Bond cleavage is also possible by a process called heterolysis. The energy involved in this process is called bond dissociation energy (BDE). BDE is defined as the "enthalpy (per mole) required to break a given bond of some specific molecular entity by homolysis," symbolized as ''D''. BDE is dependent on the strength of the bond, which is determined by factors relating to the stability of the resulting radical species. Because of the relatively high energy required to break bonds in this manner, homolysis occurs primarily under certain circumstances: * Li ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Kolbe Electrolysis
__NOTOC__ The Kolbe electrolysis or Kolbe reaction is an organic reaction named after Hermann Kolbe. The Kolbe reaction is formally a decarboxylative dimerisation of two carboxylic acids (or carboxylate ions). The overall reaction is: : If a mixture of two different carboxylates are used, all combinations of them are generally seen as the organic product structures: : 3 R1COO− + 3 R2COO− → R1−R1 + R1−R2 + R2−R2 + 6 CO2 + 6 e− The reaction mechanism involves a two-stage radical process: electrochemical decarboxylation gives a radical intermediate, which combine to form a covalent bond. As an example, electrolysis of acetic acid yields ethane and carbon dioxide: :CH3COOH → CH3COO− → CH3COO· → CH3· + CO2 :2CH3· → CH3CH3 Another example is the synthesis of 2,7-dimethyl-2,7-dinitrooctane from 4-methyl-4-nitrovaleric acid: : Further reading * * See also * Electrosynthesis * Wurtz reaction In organic chemistry, the Wurtz reaction, named ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Krapcho Decarboxylation
The Krapcho decarboxylation is the chemical reaction of esters with halide anions. The ester must contain an electron-withdrawing group in the beta position, such as β-ketoesters, malonic esters, α-cyanoesters, or α-sulfonylesters. It works best with methyl esters, since methyl groups are more susceptible to SN2-reaction than are, say, ethyl groups. The byproducts of this decarbomethoxylation are chloromethane Chloromethane, also called methyl chloride, Refrigerant-40, R-40 or HCC 40, is an organic compound with the chemical formula . One of the haloalkanes, it is a colorless, odorless, flammable gas. Methyl chloride is a crucial reagent in industrial ... and CO2. They are lost as gases, which helps drive the reaction. The Krapcho decarboxylation is a useful way to manipulate malonic esters because it cleaves only one of the two ester groups. The apparent alternative, base hydrolysis followed by decarboxylation, requires a subsequent step to regenerate the ester. : Re ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Kochi Reaction
The Kochi reaction is an organic reaction for the decarboxylation of carboxylic acids to alkyl halides with lead(IV) acetate and a lithium halide.''A New Method for Halodecarboxylation of Acids Using Lead(IV) Acetate'' Jay K. Kochi J. Am. Chem. Soc.; 1965; 87(11); 2500–02. The reaction is a variation of the Hunsdiecker reaction The Hunsdiecker reaction (also called the Borodin reaction or the Hunsdiecker–Borodin reaction) is a name reaction in organic chemistry whereby silver salts of carboxylic acids react with a halogen to produce an organic halide. It is an e .... References Organic reactions Name reactions {{organic-chemistry-stub ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Hunsdiecker Reaction
The Hunsdiecker reaction (also called the Borodin reaction or the Hunsdiecker–Borodin reaction) is a name reaction in organic chemistry whereby silver salts of carboxylic acids react with a halogen to produce an organic halide. It is an example of both a decarboxylation and a halogenation reaction as the product has one fewer carbon atoms than the starting material (lost as carbon dioxide) and a halogen atom is introduced its place. The reaction was first demonstrated by Alexander Borodin in his 1861 reports of the preparation of methyl bromide () from silver acetate (). Shortly after, the approach was applied to the degradation of fatty acids in the laboratory of Adolf Lieben. However, it is named for Cläre Hunsdiecker and her husband Heinz Hunsdiecker, whose work in the 1930s developed it into a general method. Several reviews have been published, and a catalytic approach has been developed. : History Alexander Borodin first observed the reaction in 1861 whe ... [...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 center ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chloroform
Chloroform, or trichloromethane, is an organic compound with formula C H Cl3 and a common organic solvent. It is a colorless, strong-smelling, dense liquid produced on a large scale as a precursor to PTFE. It is also a precursor to various refrigerants. It is trihalomethane. It is a powerful anesthetic, euphoriant, anxiolytic, and sedative when inhaled or ingested. Structure The molecule adopts a tetrahedral molecular geometry with C3v symmetry. Natural occurrence The total global flux of chloroform through the environment is approximately tonnes per year, and about 90% of emissions are natural in origin. Many kinds of seaweed produce chloroform, and fungi are believed to produce chloroform in soil. Abiotic processes are also believed to contribute to natural chloroform productions in soils although the mechanism is still unclear. Chloroform volatilizes readily from soil and surface water and undergoes degradation in air to produce phosgene, dichloromethane, formyl ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Tri-n-butyltin Hydride
Tributyltin hydride is an organotin compound with the formula (C4H9)3SnH. It is a colorless liquid that is soluble in organic solvents. The compound is used as a source of hydrogen atoms in organic synthesis. Synthesis and characterization The compound is produced by reduction of tributyltin oxide with polymethylhydrosiloxane: : 2 " eSi(H)Osub>n" + (Bu3Sn)2O → " eSi(OH)Osub>n" + 2 Bu3SnH The hydride is a distillable liquid that is mildly sensitive to air, decomposing to (Bu3Sn)2O. Its IR spectrum exhibits a strong band at 1814 cm−1 for ''ν''Sn−H. Applications It is a specialized reagent in organic synthesis. Combined with azobisisobutyronitrile (AIBN) or by irradiation with light, tributyltin hydride converts organic halides (and related groups) to the corresponding hydrocarbon. This process occurs via a radical chain mechanism involving the radical Bu3Sn•. [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Radical Reaction
In chemistry, a radical, also known as a free radical, is an atom, molecule, or ion that has at least one unpaired valence electron. With some exceptions, these unpaired electrons make radicals highly chemically reactive. Many radicals spontaneously dimerize. Most organic radicals have short lifetimes. A notable example of a radical is the hydroxyl radical (HO·), a molecule that has one unpaired electron on the oxygen atom. Two other examples are triplet oxygen and triplet carbene (꞉) which have two unpaired electrons. Radicals may be generated in a number of ways, but typical methods involve redox reactions. Ionizing radiation, heat, electrical discharges, and electrolysis are known to produce radicals. Radicals are intermediates in many chemical reactions, more so than is apparent from the balanced equations. Radicals are important in combustion, atmospheric chemistry, polymerization, plasma chemistry, biochemistry, and many other chemical processes. A majority o ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Azobisisobutyronitrile
Azobisisobutyronitrile (abbreviated AIBN) is an organic compound with the formula CH3)2C(CN)sub>2N2. This white powder is soluble in alcohols and common organic solvents but is insoluble in water. It is often used as a foamer in plastics and rubber and as a radical initiator. As an azo initiator, radicals resulting from AIBN have multiple benefits over common organic peroxides. For example, they do not have oxygenated byproducts or much yellow discoloration. Additionally, they do not cause too much grafting and therefore are often used when making adhesives, acrylic fibers, detergents, etc. Mechanism of decomposition In its most characteristic reaction, AIBN decomposes, eliminating a molecule of nitrogen gas to form two 2-cyanoprop-2-yl radicals: : Because azobisisobutyronitrile readily gives off free radicals, it is often used as a radical initiator. This happens at temperatures above 40 °C, but in experiments is more commonly done at temperatures between 66&nb ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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