2368-53-8Relevant academic research and scientific papers
The Pd-catalyzed coupling of allyl halides and tin aryls: Why the catalytic reaction works and the stoichiometric reaction does not
Albeniz, Ana C.,Espinet, Pablo,Martin-Ruiz, Blanca
, p. 2481 - 2489 (2001)
Arylallylpalladium complexes [Pd(5-C6F5-η3-cyclohexenyl) (C6Cl2F3) -(NCMe)] (10) and [Pd2(μ-C6Cl2F3)2 (5-C6F5-1,3-η3-cyclohexenyl) 2] (13) have been synthesized. Complex 13 is an example of a rare class of metal complexes with aryl bridges and its X-ray crystal diffraction structure has been determined. These arylallylpalladium complexes are involved in the coupling of Bu3SnRf (1, Rf=dichlorotrifluorophenyl) and [Pd2(μ-Br)2(5-C6F5-1,3- η3-cyclohexenyl)2] (2); complex 10 has been detected in the course of the stoichiometric coupling reaction in acetonitrile. Decomposition experiments of 10 and 13 in different conditions, and comparison with the reactions of 1 and 2, allow us to determine that reductive elimination does not occur in the absence of additives, p-Benzoquinone coordinates to Pd to give complex 15 and promotes reductive elimination to give the coupling products selectively. The outcome of the coupling reaction is controlled by the reductive elimination step, but the overall rate is controlled by the faster preequilibrium, which determines the concentration of 10 or 13. Palladium-catalyzed coupling of allyl halides and tin aryls works better than the stoichiometric allyl-aryl reductive coupling on isolated allylarylpalladium complexes, because they benefit from the presence in the solution of substrate allylic halides acting as electron-withdrawing olefins and promoting reductive elimination. More efficient allyl-aryl couplings, whether stoichiometric or catalytic, can be achieved upon addition of p-benzoquinone to the reaction mixture in a noncoordinating solvent.
PROCESS FOR PREPARATION OF HALO SUBSTITUTED BENZOIC ACID COMPOUND AND INTERMEDIATES THEREOF
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Page/Page column 12, (2018/09/28)
The present invention provides a process for preparation of halo substituted benzoic acid compound of Formula (1) and intermediates thereof.
Industrial production method for total halogenated derivatives
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, (2016/10/24)
The invention provides an industrial production method for total halogenated derivatives. The production method is characterized in that a target product is produced from quintozene as a raw material through the processes of fluorization, reduction and iodination. The production method provided by the invention is simple and different from a complicated production mode, strict production conditions and a serious pollution problem in the prior art.
Stable nickel catalysts for fast norbornene polymerization: Tuning reactivity
Casares, Juan A.,Espinet, Pablo,Martin-Alvarez, Jose M.,Martinez-Ilarduya, Jesus M.,Salas, Gorka
, p. 3825 - 3831 (2007/10/03)
The air-stable complexes trans-[Ni(C6Cl2F 3)2L2] (L = SbPh3, 1; AsPh 3, 2; AsCyPh2, 3; AsMePh2, 4; PPh3, 5) have been synthesized by arylation of
Reductive transformations of organofluorine compounds: II. Hydrodechlorination of chloropolyfluoroarenes by the action of zinc
Krasnov,Platonov
, p. 1488 - 1499 (2007/10/03)
Polyfluoroarenes containing chlorine atoms in the aromatic ring and/or in the benzylic position undergo hydrodechlorination by the action of zinc in aqueous dimethylformamide. The use of Zn/Cu and addition of salts (NaCl, Na2SO4, NH4Cl) favor reductive dechlorination of the Carom - Cl bond. Polyfluorobenzotrichlorides react with excess zinc to give the corresponding CH3-substituted derivatives, otherwise CH2Cl- and CHCl2-containing compounds are formed. The reduction of C6F5CCl3 and C6F5CH2Cl with zinc in the presence of copper provides lower yields of the hydrodechlorination products and leads to formation of 1,2-bis(pentafluorophenyl)ethane.
Reductive dehalogenation of polyfluoroarenes by zinc in aqueous ammonia
Laev, Sergey S.,Shteingarts, Vitalii D.
, p. 175 - 185 (2007/10/03)
Aqueous ammonia has been found to be a good and versatile medium for the highly selective hydrodehalogenation of polyfluoroarenes by zinc under unprecedentedly mild conditions. The reduction of pentafluorobenzoic acid, 2,3,4,5,6-pentafluorobenzyl alcohol, pentafluorobenzamide, pentafluoropyridine, heptafluoro-2-naphthoic acid, 1,3,4,5,7,8-hexafluoro-2-naphthoic acid, octafluoronaphthalene, octafluorotoluene, decafluorobiphenyl, chloropentafluorobenzene and 4-chlorotetrafluorobenzoic acid give products derived from the removal of one or two halogen atoms. A reduction mechanism, proceeding through electron capture to give a radical anion and then fragmentation of the latter, has been suggested. The observed high selectivity of the process suggests a radical anion formed by direct electron transfer from zinc to substrate. The dehalogenation regioselectivity is basically in accordance with that expected for radical anion fragmentation.
SYNTHETIC ASPECTS OF THE HYDROGENOLYSIS OF ORGANOFLUORINE COMPOUNDS UNDER THE INFLUENCE OF Zn(Cu)
Platonov, V. E.,Krasnov, V. I.
, p. 1336 - 1340 (2007/10/02)
We used the system containing Zn(Cu) in DMFA-water for the synthesis of monohydro derivatives from perfluoroarenes, for the selective hydrogenolysis of the C-Cl bonds, and for the formation of the substituent CH2CF3 by transformation of the CF(CF3)2 group
LA FLUORATION PAR KF DE PERHALOGENES ORGANIQUES AROMATIQUES EN PRESENCE DE FAIBLES QUANTITES DE SULFOLANE OU D'EAU. SPECTRES DE MASSES DES MELANGES OBTENUS EN SERIE BENZENIQUE
Hitzke, J.
, p. 101 - 116 (2007/10/02)
The fluorinations of perhalogenated aromatic compounds with KF are carried out in sealed tubes in presence of inert gas.The addition of small quantities of aprotic solvent promotes the fluorination of pentachloropyridine above 180 deg C; these fluorinatio
