- Ruthenium sulfophthalocyanine catalyst for the oxidation of chlorinated olefins with hydrogen peroxide
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In aqueous solution and at room temperature, various α-chloro-alkenes are effectively dechlorinated by hydrogen peroxide oxidation using a water-soluble ruthenium(II)-tetrasulfophthalocyanine catalyst, RuPcS. The molecular structure of RuPcS has been elucidated by ESI-mass spectroscopy. In the reaction conditions, and specifically in acidic media, the complex rapidly gives rise to a novel species, most likely catalytically active, whose nature is investigated.
- Bressan, Mario,Celli, Nicola,D'Alessandro, Nicola,Liberatore, Lolita,Morvillo, Antonino,Tonucci, Lucia
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Read Online
- Hydration of Alkynes to Ketones with an Efficient and Practical Polyoxomolybdate-based Cobalt Catalyst
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Hydration of alkynes to ketones is one of the most atom economical and universal methods for the synthesis of carbonyl compounds. However, the basic reaction usually requires organic ligand catalysts or harsh reaction conditions to insert oxygen into the C≡C bond. Here, we report an inorganic ligand supported cobalt (III) catalyst, (NH4)3[CoMo6O18(OH)6], which is supported by a central cobalt (III) mononucleus and a ring-shaped pure inorganic ligand composed of six MoVIO6 octahedrons to avoid the disadvantages of expensive and unrecyclable organic ligand catalysts or noble metal catalysts. Under mild conditions, the cobalt (III) catalyst can be used for the hydration of alkynes to ketones. The catalyst is non-toxic, green, and environment friendly. The catalyst can be recycled at least six times with high activity. According to control experiments, a reasonable mechanism is provided.
- Xie, Ya,Wang, Jingjing,Wang, Yunyun,Han, Sheng,Yu, Han
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p. 4985 - 4989
(2021/10/12)
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- A kind of 3,4-dichloro-thiazole derivatives and process for their preparation and use
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The invention provides 3,4-dichloro isothiazole derivatives, their preparation method and application. The invention relates to a heterocyclic compound containing 3,4-dichloro isothiazol, and the compound is represented by the following chemical structural general formula. The invention discloses the structural general formula of the compound, a synthetic method of the compound and applications of the compound as pesticide, bactericide, anti-plant virus agent, and plant activator, and a technology of mixing the compound with agriculturally acceptable auxiliary agents or synergists for preparing pesticide, bactericide, anti-plant virus agent, and plant activator. The invention further discloses the combined application of the compound and the commercial pesticide, bactericide, anti-plant virus agent, and plant activator in controlling diseases, insect pests, and virus diseases in agriculture, forestry and gardening, and a preparation method of the compound and the commercial pesticide, bactericide, anti-plant virus agent, and plant activator.
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Paragraph 0042-0043; 0093-0094
(2016/10/08)
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- A mild method for the replacement of a hydroxyl group by halogen. 1. Scope and chemoselectivity
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α-Chloro-, bromo- and iodoenamines, which are readily prepared from the corresponding isobutyramides have been found to be excellent reagents for the transformation of a wide variety of alcohols or carboxylic acids into the corresponding halides. Yields are high and conditions are very mild thus allowing for the presence of sensitive functional groups. The reagents can be easily tuned allowing therefore the selective monohalogenation of polyhydroxylated molecules. The scope and chemoselectivity of the reactions have been studied and reaction mechanisms have been proposed.
- Munyemana, Fran?ois,George, Isabelle,Devos, Alain,Colens, Alain,Badarau, Eduard,Frisque-Hesbain, Anne-Marie,Loudet, Aurore,Differding, Edmond,Damien, Jean-Marie,Rémion, Jeanine,Van Uytbergen, Jacqueline,Ghosez, Léon
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p. 420 - 430
(2015/12/31)
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- Chlorination of various substrates in subcritical carbon tetrachloride
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Various aliphatic hydrocarbons and the side chains of aromatic hydrocarbons were chlorinated in subcritical carbon tetrachloride. Chlorination of aromatic compounds including 1,4-disubstituted benzenes was investigated. Ketones and sulfones were stable under the employed conditions. Sulfoxides were converted into sulfides in a low to modest yields. The coupling adducts between olefins and carbon tetrachloride were obtained from the reactions of olefins.
- Tanemura, Kiyoshi,Suzuki, Tsuneo,Nishida, Yoko,Horaguchi, Takaaki
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experimental part
p. 2881 - 2888
(2010/06/16)
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- Chlorination of aliphatic hydrocarbons, aromatic compounds, and olefins in subcritical carbon tetrachloride
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The reactions of various substrates including aliphatic hydrocarbons, aromatic compounds, and olefins were investigated in subcritical carbon tetrachloride. Ketones and sulfones were stable under the employed conditions. The coupling adducts between olefins and carbon tetrachloride were obtained from the reactions of olefins.
- Tanemura, Kiyoshi,Suzuki, Tsuneo,Nishida, Yoko,Horaguchi, Takaaki
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scheme or table
p. 6419 - 6422
(2009/04/06)
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- The effects of ring size and substituents on the rates of acid-catalysed hydrolysis of five- and six-membered ring cyclic ketone acetals
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A series of sterically similar five- and six-membered ring cyclic diol-derived ketone acetals have been prepared and their rates of acid-catalysed hydrolysis examined. The rates of hydrolysis are substantially affected by acetal ring conformational stereoelectronic effects and resonance effects depending upon the substituents on the parent ketone; an A1 mechanism of hydrolysis explains the observed effects. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Knowles, Jonathan P.,Whiting, Andrew
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p. 3365 - 3368
(2008/02/10)
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- Rate coefficients and mechanisms of the reaction of Cl-atoms with a series of unsaturated hydrocarbons under atmospheric conditions
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The rate coefficients and mechanisms of the reaction of Cl-atoms with a series of unsaturated hydrocarbons under atmospheric conditions were studied. It was observed the product yielded from both trans-2-butene and 1-butene were found to be oxygen dependent. The results showed that the variation of the product yielded with O2 in the case of 1-butene resulted from competitive reaction pathways for the two β-chlorobutoxy radicals involved in the oxidation.
- Orlando, John J.,Tyndall, Geoffrey S.,Apel, Eric C.,Riemer, Daniel D.,Paulson, Suzanne E.
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p. 334 - 353
(2007/10/03)
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- Allenylsilanes fonctionnels: synthese regioselective par voie organoaluminique d'alcools alleniques trimethylsilyles α'- ou ω'-chlores
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In many cases, the reaction between α- or ω-chloro carbonyl derivatives and organoaluminium compound prepared from Me3Si-CC-CH2Br is chemo- and regioselective: it affords, in a good yield, trimethylsilyl α-allenyl alcohols α'- or ω'-substituted by a chlorine atom; some of these functional alcohols have produced oxygenated heterocycles.
- Mesnard, Danielle,Miginiac, Leone
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p. 299 - 309
(2007/10/02)
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- Novel Regioselective Chlorination of Aliphatic Ketones via Mono-organothallium(III) Derivates
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Room temperature reaction of simple aliphatic ketones with an aqueous solution of TiCl3 leads to mono-oxoalkylthalium(III) derivatives followed by formation of selectively α-monochlorinated ketones.
- Glaser, Julius,Toht, Imre
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p. 1336 - 1337
(2007/10/02)
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- CHLORINATION OF KETONES WITH TRICHLOROISOCYANURIC ACID
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Trichloroisocyanuric acid is an effective reagent for the chlorination of ketones in the alpha position.
- Hiegel, Gene A.,Peyton, Kim B.
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p. 385 - 392
(2007/10/02)
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- Chlorination of Aliphatic Ketones in Methanol
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The chlorination of aliphatic ketones in methanol has been examined.The product distributions in methanol differ substantially from those obtained by chlorination in carbon tetrachloride.The reaction in methanol favors addition of chlorine to the least substituted carbon α to the carbonyl group.The effect is especially pronounced if an α carbon bearing two substituents is present.The distribution of products is determined by the relative stability of the enol ethers formed from the ketone under the reaction conditions.
- Gallucci, R. R.,Going, R.
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p. 2532 - 2538
(2007/10/02)
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- INVESTIGATION IN THE FIELD OF UNSATURATED COMPOUNDS VI. LIQUID-PHASE CHLORINATION OF 2-HALOGENO-2-BUTENES
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The liquid-phase chlorination of 2-halogeno-2-butenes in the presence of tert-butylpyrocatechol leads to the formation of the products from an anomalous reaction (2,3-dihalogeno-1-butenes), substitution of hydrogen at the double bond (2,3-dihalogeno-2-butenes), and normal addition (2,2,3-trihalogenobutanes).The ratios of these compounds are 70:6:24 in the case of 2-chloro-2-butene and 54:7.5:38.5 in the case of 2-bromo-2-butene.During the chlorination of 2-chloro-2-butene in the presence of sodium bicarbonate the formation of 3-chloro-2-butanol (20percent) was observed as a result of the combined addition of chlorine and water.
- Mkryan, G. G.,Kaplanyan, E. E.,Mkryan, G. M.
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p. 1833 - 1836
(2007/10/02)
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- Halogen Epoxides, 3. Reactions of 2-Chloro- and 2,3-Dichlorooxiranes with Silver Tetrafluoroborate: Synthesis of α-Fluorinated Carbonyl Compounds
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Reactions of chlorinated oxiranes with silver tetrafluoroborate in ether have been investigated.Substituted-2-chlorooxiranes (4a - e) afforded the corresponding α-fluorocarbonyl compounds (7a - e) as major products and the isomeric α-chlorocarbonyl compounds (8a - e) as minor products.Substituted 2,3-dichlorooxiranes (10, 14, 20, 24) yielded the isomeric α,α-dichloroketones (13, 19, 22, 26b, 29b) as well as the corresponding α-chloro-α-fluoroketones (12, 17, 21, 26a, 29a) and α,β-unsaturated α-chloroketones (18, 23, 27, 30).The course of the reaction was rationalized.Similar reaction with α-chloroketones and with α,α-dichloroketones succeeded only at substrates (8b, 35) in which the chlorine substituents were in benzylic positions.
- Griesbaum, Karl,Keul, Helmut,Kibar, Riza,Pfeffer, Bernd,Spraul, Manfred
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p. 1858 - 1870
(2007/10/02)
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- REACTION OF α-NITRO EPOXIDES WITH HYDROHALIC ACIDS AND THEIR SALTS
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The reaction of α-nitro epoxides of the aliphatic series with hydrohalic acids and their salts leads to the formation of the corresponding α-halogencarbonyl compounds.
- Sokolov, N. A.,Tishchenko, I. G.,Kovganko, N. V.
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p. 248 - 250
(2007/10/02)
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