- Synthesis, structure, and reactivity of C-isopropyl-ortho-carborane organoboron derivatives
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A reaction of isopropyl-ortho-carborane with n-butyllithium, followed by treatment of the lithium derivative formed with boron trichloride, chlorodimethoxyborane, or chloropinacolatoborane furnished C-boryl-ortho-carboranes 1a-c. Further functionalization
- Svidlov,Voloshin, Ya. Z.,Yurgina,Potapova,Belyy, A. Yu.,Ananyev,Bubnov, Yu. N.
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- PHOTO LEWIS ACID GENERATOR
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Provided is a compound capable of generating a Lewis acid in response to light unlike conventional photo acid generators. The compound comprises an anionic moiety having a central boron atom and a particular cationic moiety (for example, a cation having a HOMO-LUMO gap of 5.3 eV or less). The cationic moiety may, for example, have a skeleton selected from an N-substituted pyridinium skeleton, an N-substituted bipyridinium skeleton, an N-substituted quinolinium skeleton, and a pyrylium skeleton.
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Paragraph 0104-0107; 0137-0139
(2020/03/09)
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- Preparation method of anhydrous tris (pentafluorophenyl) borane (by machine translation)
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The raw materials are easily obtained, the production cost is reduced, the workload of post-treatment is reduced, the process operation is simple, the reaction time is effectively shortened, and the purity and the yield of the target product are improved. (by machine translation)
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Paragraph 0038; 0039; 0041; 0042; 0044; 0045; 0047; 0048
(2020/10/21)
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- Preparation of heptafluoronaphthyllithiums and -magnesiums: An unexpected difference in the reactivity of isomers C10F7H and C10F7Br towards organolithium and organomagnesium compounds
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Significant differences in the reactivity of isomeric heptafluoronaphthalenes and bromoheptafluoronaphthalenes towards organolithium and organomagnesium compounds were found. Metalation of polyfluorinated naphthalenes 2-C10F7X (X = H, Br) occurs easily under the action of bases (BuLi, t-BuLi, LDA) as well as EtMgBr (X = Br) in ether. This fact was proven by 19F NMR spectroscopy and by trapping of 2-C10F7M (M = Li, MgBr, Mg(2-C10F7)) with electrophile ClSiMe3. The interaction of 1-C10F7Br with BuLi or EtMgBr proceeds in a similar way. In contrast to 2-C10F7H, isomeric 1-C10F7H is the less acidic substrate and undergoes only the nucleophilic alkyldefluorination when combined with BuLi or t-BuLi.
- Shmakov, Mikhail M.,Bardin, Vadim V.,Prikhod'ko, Sergey A.,Adonin, Nicolay Yu
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supporting information
(2019/08/20)
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- Transmetalation of Pentafluorophenylmercury Derivatives with Organylmagnesium Bromides
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The reactions of pentafluorophenylmercury derivatives with organomagnesium compounds have been studied. The interaction of pentafluorophenylmercury chloride with RMgBr (R = Et, Ph) has afforded diphenyl- and diethylmercury or phenylmercury chloride, besides the expected product (C6F5HgR). The results have been explained by the transmetalation of C6F5HgR with the Grignard reagent, followed by the reaction of the resulting C6F5MgX (X = Br, C6F5) with pentafluorophenylmercury chloride. Transmetalation of (C6F5)2Hg with organylmagnesium bromides has led to the formation of C6F5MgX and R2Hg.
- Bardin
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p. 1406 - 1408
(2019/08/21)
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- Bi- and tridentate silicon-based acceptor molecules
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Triethynylphenylsilane (1), trivinylphenylsilane (2), diethynyldiphenylsilane (3) and diphenyldivinylsilane (4) were reacted with chlorodimethylsilane yielding the corresponding hydrosilylation products. To increase their Lewis acidity, the Si-Cl functions were directly transferred into Si-C6F5 units by salt elimination reactions leading to the (semi-) flexible molecules 5-8 bearing two or three Lewis-acidic sidearms. With the aim of providing host-guest complexes, the air-stable and readily soluble compounds 5-8 were converted with N- and O-Lewis bases of different size and geometry. In all cases, NMR spectroscopic investigations reveal no formation of Lewis acid-base complexes. X-ray diffraction experiments of host compounds 5-7 show intermolecular aryl perfluoroaryl interactions of dispersion nature in the solid state. By hydrosilylation of 1 with trichlorosilane the more Lewisacidic all-trans-tris[(trichlorosilyl)vinyl]phenylsilane (9) was obtained. Its Lewis acidity was further increased by fluorination to yield all-trans-tris[(trifluorosilyl)vinyl] phenylsilane (10); the conversion with nitrogen containing Lewis bases ends up in the formation of insoluble precipitates.
- Horstmann, Jan,Lamm, Jan-Hendrik,Strothmann, Till,Neumann, Beate,Stammler, Hans-Georg,Mitzel, Norbert W.
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p. 383 - 391
(2017/06/30)
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- Asymmetric 1,2-Perfluoroalkyl Migration: Easy Access to Enantioenriched α-Hydroxy-α-perfluoroalkyl Esters
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This study has led to the development of a novel, highly efficient, 1,2-perfluoro-alkyl/-aryl migration process in reactions of hydrate of 1-perfluoro-alkyl/-aryl-1,2-diketones with alcohols, which are promoted by a Zn(II)/bisoxazoline and form α-perfluoro-alkyl/-aryl-substituted α-hydroxy esters. With (-)-8-phenylmenthol as the alcohol, the corresponding menthol esters are generated in high yields with excellent levels of diastereoselectivity. The mechanistic studies show that the benzilic ester-type rearrangement reaction takes place via an unusual 1,2-migration of electron-deficient trifluoromethyl group rather than the phenyl group. The overall process serves as a novel, efficient, and simple approach for the synthesis of highly enantioenriched, biologically relevant α-hydroxy-α-perfluoroalkyl carboxylic acid derivatives.
- Wang, Pan,Feng, Liang-Wen,Wang, Lijia,Li, Jun-Fang,Liao, Saihu,Tang, Yong
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supporting information
p. 4626 - 4629
(2015/04/27)
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- PLATINUM COMPLEXES
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The invention aims at providing platinum complexes useful as materials for light emitting devices and extremely excellent in heat stability, luminous characteristics, and luminous efficiency, and a process for effective preparation thereof. The invention relates to platinum complexes represented by the general formula [1]: wherein any two of A, B and C are each independently an optionally substituted nitrogenous aromatic heterocyclic group and the other is optionally substituted aryl or optionally substituted heteroaryl; and Y is halogeno or an optionally substituted aryl or heteroaryl group which is bonded either directly or through oxygen (-O-) or sulfur (-S-) (with the proviso that when the adjacent two rings are nitrogenous aromatic heterocyclic groups, the cases wherein Y is chloro are excepted, while when the nonadjacent two rings are nitrogenous aromatic heterocyclic groups, the cases wherein Y is not halogeno are excepted).
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Page/Page column 37
(2008/06/13)
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- Process for preparing a tetrakis(fluoroaryl) borate derivative
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A fluoroaryl magnesium derivative expressed by General Formula (1): where each of R1-R5represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group while at least one of R1-R5representing a fluorine atom, and Xa represents a chlorine atom, a bromine atom, or an iodine atom; and boron halide expressed by General Formula (2): BXb3??(2) ?where Xb represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are reacted with each other in a solvent (a) containing diethyl ether and/or tetrahydrofuran, after which the resulting reaction solution is added to a solvent (b) having a higher boiling point than diethyl ether and/or tetrahydrofuran while diethyl ether and/or tetrahydrofuran are distilled out. Consequently, it has become possible to obtain a (fluoroaryl)borane compound expressed by General Formula (3): ?where each of R1-R5, and Xb, represents the same as above, and n represents 2 or 3, from which magnesium halide produced as a by-product is separated and removed, selectively in a simple manner at a low cost.
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Page column 32-33; 34-35
(2008/06/13)
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- Method for producing tetrakis ( fluoroaryl) borate-magnesium compound
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Fluoroaryl magnesium halide is reacted with a boron compound so that a molar ratio of the fluoroaryl magnesium halide to the boron compound is not less than 3.0 and not more than 3.7, so as to produce a tetrakis (fluoroaryl) borate·magnesium compound. With this method, there occurs no hydrogen fluoride which corrodes a producing apparatus and requires troublesome waste water treatment.
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- Process for producing fluoroaromatic carboxylates
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This invention describes processes for producing halomagnesium fluoroaryl carboxylates. In one such process, a fluoroaryl Grignard reagent is added to an anhydrous liquid ethereal medium pretreated with carbon dioxide.
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Page column 8
(2010/01/31)
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- Method for producing fluoroaryl metal compound
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A method for easily and inexpensively producing and purifying a fluoroaryl metal compound such as bis(pentafluorophenyl)dialkyltin which is less colored and has no impurities is provided. Hydrocarbon magnesium halide is reacted with fluoroaryl halide in a
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- Method of making chlorofluoroethers
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A method is provided for preparation of chlorofluoroethers ClCF2CFClOR8f and Cl2CFCFClOR8f by direct fluorination of Cl2CHCH2OR8 and Cl3CCH2OR8, respectively, wherein R8 is a C1-C20 alkyl-or acyl-containing group optionally up to 5 ether oxygen atoms and optionally substituted by functional groups and R81, is the corresponding perfluoroalkyl or perfluoracyl-containing group.
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- Method for manufacturing fluoroaryl magnesium halide
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In order to provide a method of safely, efficiently, and industrially manufacturing fluoroaryl magnesium halide containing no impurities, such as coloring components, by a relatively gradual reaction compared with the conventional reactions, and a method of readily and efficiently manufacturing a highly-pure fluoroaryl borane derivative, fluoroaryl magnesium halide expressed by General Formula (1): where each of R1-R5independently represents H, F, a hydrocarbon group, or an alkoxy group, provided that at least three of R1-R5are fluorine atoms, and Xarepresents Cl, Br, or I; is manufactured by reacting, in a solvent containing a chain ether solvent, hydrocarbon magnesium halide expressed by General Formula (2): R6MgXa??(2) where R6represents a hydrocarbon group, and Xarepresents Cl, Br, or I; with fluoroaryl halide expressed by General Formula (3): where each of R1-R5independently represents H, F, a hydrocarbon group, or an alkoxy group, provided that at least three of R1-R5are fluorine atoms and Xbrepresents Br or I.
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- Process for preparing fluoroaryl magnesium derivative and process for preparing (fluoroaryl) borane compound
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A fluoroaryl magnesium derivative is produced by reacting aryl fluoride, hydrocarbon halide, and magnesium with one another in an ether solvent or a mixed solvent of the ether solvent and a hydrocarbon solvent. Also, a (fluoroaryl)borane compound is produced by mixing both a solution prepared by dissolving the fluoroaryl magnesium derivative into the ether solvent and another solvent prepared by dissolving the boron halide in the ether solvent with a hydrocarbon solvent having a higher boiling point than the ether solvent, so that the fluoroaryl magnesium derivative and boron halide react with each other while the ether solvent is being distilled out.
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- Bromine-magnesium-exchange as a general tool for the preparation of polyfunctional aryl and heteroaryl magnesium-reagents
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The scope of the Br-Mg-exchange reaction for the preparation of polyfunctional aryl and heteroaryl magnesium reagents has been studied. Various functional groups (ester, cyano, bromide) were tolerated in the exchange reaction allowing the preparation of polyfunctional Mg-reagents. Several dibromo- or tribromoheterocycles undergo a chemoselective mono-Br-Mg exchange leading to highly functionalized heterocycles.
- Abarbri, Mohamed,Dehmel, Florian,Knochel, Paul
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p. 7449 - 7453
(2007/10/03)
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- Halogenated acrylates and polymers derived therefrom
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Acrylates having a high degree of halogenation, as well as polymers that include one or more mer units derived from such acrylates provide materials having tailorable optical and physical properties. The polymers find utility particularly in optical devic
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- Producing process of (fluoroaryl) borane compound and producing process of tetrakis (fluoroaryl) borate derivative
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A fluoroaryl magnesium derivative expressed by General Formula (1): where each of R1-R5represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group while at least one of R1-R5representing a fluorine atom, and Xa represents a chlorine atom, a bromine atom, or an iodine atom; and, ???boron halide expressed by General Formula (2) : BXb3where Xb represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, are reacted with each other in a solvent (a) containing diethyl ether and/or tetrahydrofuran, after which the resulting reaction solution is added to a solvent (b) having a higher boiling point than diethyl ether and/or tetrahydrofuran while diethyl ether and/or tetrahydrofuran are distilled out. Consequently, it has become possible to obtain a (fluoroaryl)borane compound expressed by General Formula (3): where each of R1-R5represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group while at least one of R1-R5representing a fluorine atom, Xb represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and n represents 2 or 3, from which magnesium halide produced as a by-product is separated and removed, selectively in a simple manner at a low cost.
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- Hydrogen-1, carbon-13, and phosphorus-31 nuclear magnetic resonance spectral studies of some phenyl- and perflurorphenyl-substituted aminophosphines and aminophosphonium salts
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1H, 13C, and 31P NMR data have been acquired for the aminophosphine (i-C3H7)NHP(C6H5)2, 1, the new aminophosphines (i-C3H7)NHP(C6Fsub
- Cowley, Alan H.,Cushner, Mike,Fild, Manfred,Gibson, J. Andrew
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p. 1851 - 1855
(2008/10/08)
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