693-04-9Relevant articles and documents
Disposable cartridge concept for the on-demand synthesis of turbo Grignards, Knochel–Hauser amides, and magnesium alkoxides
Adamo, Andrea,Berton, Mateo,McQuade, D. Tyler,Sheehan, Kevin
supporting information, p. 1343 - 1356 (2020/07/10)
Magnesium organometallic reagents occupy a central position in organic synthesis. The freshness of these compounds is the key for achieving a high conversion and reproducible results. Common methods for the synthesis of Grignard reagents from metallic magnesium present safety issues and exhibit a batch-to-batch variability. Tubular reactors of solid reagents combined with solution-phase reagents enable the continuous-flow preparation of organomagnesium reagents. The use of stratified packed-bed columns of magnesium metal and lithium chloride for the synthesis of highly concentrated turbo Grignards is reported. A low-cost pod-style synthesizer prototype, which incorporates single-use prepacked perfluorinated cartridges and bags of reagents for the automated on-demand lab-scale synthesis of carbon, nitrogen, and oxygen turbo magnesium bases is presented. This concept will provide access to fresh organomagnesium reagents on a discovery scale and will do so independent from the operator’s experience in flow and/or organometallic chemistry.
Electron-Catalyzed Coupling of Magnesium Amides with Aryl Iodides
Kiriyama, Kazuya,Okura, Keisho,Tamakuni, Fumiko,Shirakawa, Eiji
supporting information, p. 4519 - 4522 (2018/03/13)
An electron was found to catalyze the coupling of magnesium diarylamides with aryl iodides giving triarylamines through a radical-anion intermediate. The transformation requires no transition metal catalysts or additives, and a wide array of products are formed in good-to-excellent yields.
PROCATALYST FOR POLYMERIZATION OF OLEFINS
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Page/Page column 23, (2018/06/16)
The present invention relates to a procatalyst comprising the compound represented by formula A as an internal electron donor, Formula A wherein R is hydrogen or a methyl group, N is nitrogen atom; O is oxygen atom; and C is carbon atom. The present invention also relates to a process for preparing said polymerization procatalyst and to a polymerization catalyst system comprising said procatalyst, a co-catalyst and optionally an external electron donor. Furthermore, the present invention relates to a polyolefin obtainable by the process according to the present invention and to the use of the compound of formula A as in internal electron donor in catalysts for polymerization of olefins.
Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgC?LiCl
Schnegelsberg, Christoph,Bachmann, Sebastian,Kolter, Marlene,Auth, Thomas,John, Michael,Stalke, Dietmar,Koszinowski, Konrad
supporting information, p. 7752 - 7762 (2016/06/08)
Grignard reagents RMgCl and their so-called turbo variant, the highly reactive RMgC?LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity-enhancing effect. A combination of electrospray-ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion-ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgC?LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron-rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents.
Catalyst system for polymerisation of an olefin
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Paragraph 0124, (2015/03/03)
The present invention relates to a catalyst system comprising a procatalyst, a co-catalyst and an external electron donor, wherein the external electron donor comprises a compound having the structure according to Formula I: ????????Si (L)n (OR1)4-n?????(Formula I), wherein, Si is a silicon atom with valency 4+; O is an oxygen atom with valency 2- and O is bonded to Si via the silicon-oxygen bond; n is 1, 2, 3 or 4; R1 is a selected from the group consisting of linear, branched and cyclic alkyl having at most 20 carbon atoms and aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms; L is a group represented by Formula II wherein, L is bonded to the silicon atom via the nitrogen-silicon bond; L has a single substituent on the nitrogen atom, where this single substituent is an imine carbon atom; and X and Y are independently selected from the group consisting of a hydrogen atom; a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements; a linear, branched and cyclic alkyl having at most 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements and an aromatic substituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms, optionally containing a heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements.
Steric parameters for substituents bound to atoms of silicon and some other elements of the third period
Ploom, Anu,Tuulmets, Ants,Jaerv, Jaak
experimental part, p. 2503 - 2510 (2011/02/25)
The kinetics of a tetraethoxysilane reaction with n-butylmagnesium chloride, stoichiometrically monosolvated with isopropyl ether or with methyl tert-butyl ether, was studied in toluene. The pseudo-first-order rate constants determined at a great excess of Grignard reagent were used for separation of the appropriate equilibrium and rate constants. Equilibrium constants for five alkyl ether ligands at the magnesium center are in an excellent correlation with isosteric ES(Si) parameters. It was concluded that these constants should be applicable to all elements of the third period of the periodic table. Taylor & Francis Group, LLC.
AMINOSILANE COMPOUNDS, CATALYST COMPONENTS AND CATALYSTS FOR OLEFIN POLYMERIZATION, AND PROCESS FOR PRODUCTION OF OLEFIN POLYMERS WITH THE SAME
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Page/Page column 18, (2010/11/30)
A catalyst for polymerization of olefins formed from (A) a solid catalyst component containing magnesium, titanium, halogen, and an electron donor compound, (B) an organoaluminum compound shown by the formula, R6pAlQ3-p, and (C) an aminosilane compound shown by the formula, R3nSi(NR4R5)4-n; and a process for producing a catalyst for polymerization of olefins in the presence of the catalyst are provided. A novel aminosilane compound, a catalyst component for polymerization of olefins having a high catalytic activity, capable of producing polymers with high stereoregularity in a high yield, and exhibiting an excellent hydrogen response, a catalyst, and a process for producing olefin polymers using the catalyst are provided.
Method of preparation of an alkyne with an optically active hydroxyl group in the beta or gamma position of a triple bond and intermediates obtained
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Page/Page column 6-7, (2010/11/25)
The present invention relates to a method of preparation of an alkyne with an optically active hydroxyl group in the β or γ position of a triple bond and intermediates obtained. The method of the invention for preparation of an alkyne with an optically active hydroxyl group in the β position of a triple bond is characterized in that it comprises the reaction, in the presence of a Lewis acid: of a compound of formula (IV): in which: R is a linear or branched alkyl group having from 1 to 6 carbon atoms. and of a compound of formula (V): [in-line-formulae]R′—C≡C-M ??(V) [/in-line-formulae]in which: R′ represents a hydrogen atom, a linear or branched alkyl group having from 1 to 8 carbon atoms, preferably a methyl group or a trialkylsilyl group. M represents a metal, preferably a metal of group (Ia) of the periodic table, preferably lithium. Another object of the invention comprises the production of an alkyne with an optically active hydroxyl group in the γ position of a triple bond by isomerization of an alkyne with an optically active hydroxyl group in the β position previously obtained.
PROCESS FOR PRODUCING PHOSPHONIUM BORATE COMPOUND, NOVEL PHOSPHONIUM BORATE COMPOUND, AND METHOD OF USING THE SAME
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Page/Page column 89-90, (2008/06/13)
The invention relates to a phosphonium borate compound represented by Formula (I) (hereinafter, the compound (I)). The invention has objects of providing (A) a novel process whereby the compound is produced safely on an industrial scale, by simple reaction operations and in a high yield; (B) a novel compound that is easily handled; and (C) novel use as catalyst. ????????Formula (I) : (R1)(R2)(R3)PH·BAr4?????(I) wherein R1, R2, R3 and Ar are as defined in the specification. The process (A) includes reacting a phosphine with a) HCl or b) H2SO4 to produce a) a hydrochloride or b) a sulfate; and reacting the salt with a tetraarylborate compound. The compound (B) has for example a secondary or tertiary alkyl group as R1 and is easily handled in air without special attention. The use (C) is characterized in that the compound (I) is used instead of an unstable phosphine compound of a transition metal complex catalyst for catalyzing C-C bond, C-N bond and C-O bond forming reactions and the compound produces an effect that is equal to that achieved by the transition metal complex catalyst.
HALIDE REDUCTION DIHYDROCARBYLMAGNESIUM MIXTURES
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Page/Page column 21, (2008/06/13)
This invention provides a process for reducing the amount of soluble halide in a solution comprising a liquid organic medium, at least one viscosity reducing agent, at least one dihydrocarbylmagnesium compound, and an initial amount of soluble halide. The process comprises mixing at least one alkali metal with the solution at a mole ratio of alkali metal to magnesium of less than about 1:2.5, thereby forming precipitated soluble halides. Also provided by this invention is a process for reducing the amount of soluble halide in a slurry comprising a liquid organic medium, at least one viscosity reducing agent, at least one dihydrocarbylmagnesium compound, solids from the formation of said dihydrocarbylmagnesium compound, and an initial amount of soluble halide. This process comprises mixing at least one alkali metal with the slurry at a mole ratio of alkali metal to magnesium of less than about 1:1.25, thereby forming precipitated soluble halides.
