- Preparation method of beta-ketosulfoxide based on CaC2 catalysis
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The invention provides a preparation method of beta-ketosulfoxide based on CaC2 catalysis, and belongs to the technical field of organic synthesis. In the presence of CaC2 or NaH or in the co-presence of CaC2 and TEA, acyl chloride and dimethyl sulfoxide react to prepare the beta-ketosulfoxide compound, the yield of beta-ketosulfoxide is 8.7-78%, and the yield of beta-ketosulfoxide in the reaction process of acyl chloride and dimethyl sulfoxide is remarkably improved. Particularly, in the coexistence of CaC2 and TEA, acyl chloride and dimethyl sulfoxide react to prepare the beta-ketosulfoxide compound, the yield of beta-ketosulfoxide is 45-78%, and the preparation method is green, environmentally friendly, mild in reaction process and simple to operate.
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Paragraph 0097-0105
(2021/06/12)
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- Thiol-free chemoenzymatic synthesis of β-ketosulfides
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A preparation of β-ketosulfides avoiding the use of thiols is described. The combination of a multicomponent reaction and a lipase-catalysed hydrolysis has been developed in order to obtain high chemical diversity employing a single sulfur donor. This methodology for the selective synthesis of a set of β-ketosulfides is performed under mild conditions and can be set up in one-pot two-step and on a gram-scale.
- Heredia, Adrián A.,López-Vidal, Martín G.,Kurina-Sanz, Marcela,Bisogno, Fabricio R.,Pe?é?ory, Alicia B.
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p. 378 - 387
(2019/02/20)
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- A convenient synthesis of novel 2,8-disubstituted pyrido[3,4-b]pyrazines possessing biological activity
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A regioselective synthetic route to 2,8-disubstituted pyrido[3,4-b] pyrazines, by initial condensation reaction between suitable diaminopyridines and α-keto aldehydes equivalents, has been developed. Focusing on the functionalization on C-8, 2-aryl-8-bromo- and 8-amino-2-arylpyrido[3,4-b] pyrazines have been synthesized. Anilines, amides, and ureas have been introduced at the 8-position from key intermediates. 2,8-Disubstituted pyrido[3,4-b]pyrazines thus prepared were found to be of biological interest. Georg Thieme Verlag Stuttgart. New York.
- Antoine, Maud,Gerlach, Matthias,Guenther, Eckhard,Schuster, Tilmann,Czech, Michael,Seipelt, Irene,Marchand, Pascal
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experimental part
p. 69 - 82
(2012/03/27)
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- Photofunctional Eu3+/Tb3+ hybrids through sulfoxide linkages: Coordination bonds construction, characterization and luminescence
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New kinds of organic-inorganic hybrid materials consisting of rare earth (Eu3+, Tb3+) complexes covalently bonded to a silica-based network have been obtained by a sol-gel approach. Three novel versatile molecular building blocks con
- Guo, Lei,Yan, Bing,Liu, Jin-Liang
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experimental part
p. 4933 - 4940
(2011/06/27)
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- The synthesis of chiral β-ketosulfoxides by enantioselective oxidation and their stereocontrolled reduction to β-hydroxysulfoxides
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Various chiral non-racemic β-ketosulfoxides, a class of compounds frequently used in asymmetric synthesis, were prepared in good yields by tert-butyl hydroperoxide oxidation of the corresponding sulfides in the presence of a complex between titanium and (
- Cardellicchio, Cosimo,Omar, Omar Hassan,Naso, Francesco,Capozzi, Maria Annunziata M.,Capitelli, Francesco,Bertolasi, Valerio
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p. 223 - 229
(2007/10/03)
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- Reactivity in eliminative cleavage of activated four-membered rings. The behaviour of 3-hydroxythietane derivatives
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3-Hydroxythietane derivatives undergo retro-aldol ring fission in aqueous sodium hydroxide at a rate determined by the substituent (H or Ph) at the 3 position and by the oxidation state of sulfur. Reactions occur between 4 × 104 and 5 × 105 times faster than for the open chain analogues. These rate accelerations correlate with an expression of strain energy between 41% and 33% compared with approximately 26% for alkene-forming eliminations of cyclobutanes. These differences, together with the differences in relative sensitivities to α-phenyl substitution and uniformly positive values of entropies of activation for 3-hydroxythietane derivatives, suggest a greater degree of ring cleavage in the transition structure for thietanes than for cyclobutanes. Ring fission is, however, accompanied by concomitant protonation of the leaving carbon group as evidenced by the isotope discrimination value of 1.7 for reaction of 3e. 3-Hydroxythietane itself does not undergo retro-aldol ring cleavage but rather anionic polymerisation to yield polymer 9a.
- Young, David J.,Stirling, Charles J. M.
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p. 425 - 429
(2007/10/03)
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- Radical Cleavage and Competing Photoreactions of Phenacyl Sulfides
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The photochemistry of ketones with the stuctures PhCOCH2SR, PhCOCH2S(O)R, PhCOCH2SO2R, and p-X-PhCOCH2SPh has been studied.They all give primarily acetophenone as product when irradiated in the presence of benzenethiol, which traps free phenacyl radicals formed by excited state β-cleavage.The sulfur-centered radicals give coupling products.The maximum quantum yield for β-cleavage is 0.40; apparently 60percent of the initially formed radical pairs undergo in-cage reaction.When R = methyl or butyl, some acetophenone is formed by γ-hydrogen abstraction as well.Alkyl subtituents on the α-carbon enhance the disproportionation reactions of the phenacyl radicals.Measurements of quantum yields and triplet life times (by Stern-Volmer quenching of acetophenone formation) allowed determination of rate constants for β-cleavage as follows: PhS, 1E10-1E11; MeS(O), 6 * 1E9; BuS, 1.5 * 1E8; BuSO2, 1 * 1E7 s-1.Ring substituents increase triplet lifetimes.Absorption and phosphorescence spectra indicate that the n,?* and ?,?* transitions both involve some population of the C-S ?* orbital.This mixing, together with free spin density on the excited carbonyl carbon, appears to determine the rate constant for cleavage.Radical cleavage is also very fast and efficient for p-((phenylthio)methyl)acetophenone.
- Wagner, Peter J.,Lindstrom, Michael J.
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p. 3062 - 3067
(2007/10/02)
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