- Preparation method of aromatic silicon organic compound
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The invention provides a preparation method of an aromatic silicon organic compound. The aromatic silicon organic compound is a compound as shown in a formula 3 shown in the specification, the aromatic silicon organic compound is prepared by reacting a compound as shown in a formula 1 with a compound as shown in a formula 2, and the reaction formula is as shown in the specification. In the formulas, a is selected from any integer of 0-5, n is selected from any integer of 1-6, R is selected from one of alkyl, alkoxy, fluorine, trifluoromethyl and trifluoromethoxy; m is any integer selected from 1-3, and R2 is selected from C1-C6 alkyl; a catalyst used in the reaction is MIc, MIc is iodized salt, M is metal ion, and c is selected from 1 or 2 according to the valence state of M; and magnesium is added in the reaction process. The method has the advantages of low cost, effective avoidance of heavy metal residues, simplicity and convenience in operation, high yield, mild reaction conditions and easiness in industrialization.
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Paragraph 0048-0051
(2021/07/08)
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- Oxidative 1,2-Difunctionalization of Ethylene via Gold-Catalyzed Oxyarylation
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Under the conditions of oxidative gold catalysis, exposure of ethylene to aryl silanes and alcohols generates products of 1,2-oxyarylation. This provides a rare example of a process that allows catalytic differential 1,2-difunctionalization of this feedstock chemical.
- Harper, Matthew J.,Emmett, Edward J.,Bower, John F.,Russell, Christopher A.
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supporting information
p. 12386 - 12389
(2017/09/22)
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- Gold-catalysed oxyarylation of styrenes and mono- and gem-disubstituted olefins facilitated by an iodine(III) oxidant
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1-Hydroxy-1,2-benziodoxol-3(1H)-one (IBA) is an efficient terminal oxidant for gold-catalysed, three-component oxyarylation reactions. The use of this iodine(III) reagent expands the scope of oxyarylation to include styrenes and gem-disubstituted olefins, substrates that are incompatible with the previously reported Selectfluor-based methodology. Diverse arylsilane coupling partners can be employed, and in benzotrifluoride, homocoupling is substantially reduced. In addition, the IBA-derived co-products can be recovered and recycled. The I's have it: The unprecedented use of an iodine(III) reagent as the terminal oxidant for gold-catalysed oxyarylation allows the substrate scope to be significantly expanded; in addition to monosubstituted olefins, styrenes and gem-disubstituted olefins are well tolerated (see scheme). With benzotrifluoride as solvent, unproductive homodimerisation of the arylsilane coupling partner is effectively suppressed. Copyright
- Ball, Liam T.,Lloyd-Jones, Guy C.,Russell, Christopher A.
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supporting information; experimental part
p. 2931 - 2937
(2012/04/23)
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- Regiocontrolled cobalt-catalyzed Diels-Alder reactions of silicon-functionalized, terminal, and internal alkynes
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(Chemical Equation Presented) The efficient control of the regiochemistry of the Diels-Alder adducts which are formed in excellent yields from 1,3-dienes and alkynylsilanes can be realized utilizing cobalt complexes with a pyridine-imine ligand or a dppe ligand, respectively. The application of 2-trimethylsilyloxy-1,3-butadiene leads to a very interesting cyclohexenone derivative suitable for further transformations.
- Hilt, Gerhard,Janikowski, Judith
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supporting information; experimental part
p. 773 - 776
(2009/08/19)
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- meta-directing cobalt-catalyzed diels-alder reactions
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(Chemical Equation Presented) Overcoming the ortho/para rule? The regioselectivity of Diels-Alder reactions with neutral electron demand between 1,3-dienes with alkynes can be controlled by simple cobalt diimine complexes so that the meta-substituted cycloadducts are generated in good yields and excellent regioselectivity (see scheme; DDQ=2,3-dichloro-5,6-dicyano-1,4- benzoquinone).
- Hilt, Gerhard,Janikowski, Judith,Hess, Wilfried
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p. 5204 - 5206
(2007/10/03)
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- Development of Odorless Thiols and Sulfides and Their Applications to Organic Synthesis
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Development of new odorless thiols (dodecanethiol, 4-n- heptylphenylmethanethiol, 4-trimethylsilylphenylmethanethiol, 4-trimethylsilylbenzenethiol) and an odorless sulfide (1-methylsulfanyldodecane) and their applications to dealkylation, Michael addition, Swern oxidation, and Corey-Kim oxidation are described.
- Nishide, Kiyoharu,Ohsugi, Shin-Ichi,Miyamoto, Tetsuo,Kumar, Kamal,Node, Manabu
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p. 189 - 200
(2007/10/03)
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- Arylcalcium hydrides as precursors to alkoxides and aryloxides of calcium
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Calcium atoms react with +I-substituted benzene derivatives under cocondensation conditions to yield arylcalcium hydrides. With toluene, tert-butylbenzene, and trimethyl(phenyl)silane the reaction showed no selectivity for C-H activation, resulting in the formation of each of the three possible isomers, while with m-xylene the reaction resulted in selective activation of the bond meta to the CH3 groups. Treatment of (tert-butylphenyl)calcium hydride with di- and trisubstituted phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol resulted in the formation of calcium aryloxides in yields > 95%. [Ca(2,4,6-tBu3C6H2O)2 (THF)3] crystallises from a THF solution as a distorted trigonal bipyramid, with two THF ligands in the trans-axial positions and the third THF ligand and both aryloxide groups in equatorial positions. The Ca-OAryl bond length was found to average at 2.181(3). A. The Ca-O-CAryl angles are almost linear, with Cal-O1-C1 and Ca1-O2-C19 being 173.9(3)° and 178.8(3)°, respectively, while the O1-Cal-O2 angle was determined as 157.04(12)°. A reaction between (tert-butylphenyl)calcium hydride and triphenylmethanol resulted in the formation of the corresponding monomeric calcium bis(alkoxide) Ca(OCPh3)2(THF)4 in 95% yield. The structure was determined as a distorted octahedron with the alkoxide ligands in a cis-equatorial arrangement. The Ca-O bond length was determined at 2.1609(17) A. The Ca-O-CAryl angle of 177.46(16)° is almost linear, while the O1-Cal-O1A angle was determined at 110.12(19)°. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).
- Dunne, John P.,Tacke, Matthias,Selinka, Carola,Stalke, Dietmar
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p. 1416 - 1425
(2007/10/03)
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- Bis-phosphonate compounds
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The present invention provides a pharmaceutical compound, or pharmaceutically acceptable salt thereof, for use in medicine, wherein said compound is of formula I wherein R is a pharmaceutically active moiety; Ar is an aromatic moiety; X is a linker group; and Y is a moiety comprising two phosphonate groups. Further aspects of the invention relate to a method for palliative and curative treatment of bone disorders and cancer related disorders, such as breast cancer.
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- Studies on the synthesis and biological properties of non-carrier-added [125I and 131I]-labeled arylalkylidenebisphosphonates: Potent bone-seekers for diagnosis and therapy of malignant osseous lesions
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Arylalkylidenebisphosphonates labeled with nca [125I or 131I] have been synthesized and their biological function investigated. The label was attached to the aromatic group in high yield and under mild conditions by means of iododesi
- ?rstad, Erik,Hoff, Per,Skatteb?l, Lars,Skretting, Arne,Breist?l, Knut
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p. 3021 - 3032
(2007/10/03)
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- Bis-phosphonate compounds
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The present invention provides a pharmaceutical compound, or pharmaceutically acceptable salt thereof, for use in medicine, wherein said compound is of formula I wherein R is a pharmaceutically active moiety; Ar is an aromatic moiety; X is a linker group; and Y is a moiety comprising two phosphonate groups. Further aspects of the invention relate to a method for palliative and curative treatment of bone disorders and cancer related disorders, such as breast cancer.
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- Synthetic equivalents of benzenethiol and benzyl mercaptan having faint smell: Odor reducing effect of trialkylsilyl group
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Syntheses and odor tests of the trialkylsilylated benzyl mercaptans and benzenethiols have revealed that the trimethylsilyl substituent on the benzene ring has a remarkable effect in reducing the foul smell of the parent benzyl mercaptan and benzenethiol.
- Nishide, Kiyoharu,Miyamoto, Tetsuo,Kumar, Kamal,Ohsugi, Shin-Ichi,Node, Manabu
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p. 8569 - 8573
(2007/10/03)
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- A mild and efficient protocol for the catalytic silylation of aryl bromides
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New catalyst systems were developed which facilitate palladium-catalyzed silylation of various functionalized aryl and heteroaryl bromides with hexamethyldisilane under unprecedented mild conditions. The use of two different sets of ligands and bases for electron-rich and electron-poor substrates, respectively, is crucial for achieving excellent product selectivities at 100 °C and atmospheric pressure. For electron-rich substrates, diphenyl-2'-pyridylphosphine in combination with K2CO3 gives the best results, whereas for electron-poor substrates, 2-(di-t-butylphosphino)biphenyl/KF is preferred. Even base-sensitive arylsilanes, which are inaccessible by the traditional routes via organolithium species or Grignard reagents, can be prepared in a single step and high yields.
- Goossen,Ferwanah
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p. 1801 - 1803
(2007/10/03)
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- The gas-phase reactivity of p-Me3Si-substituted 1,3-diphenylpropane towards charged electrophiles: Intra- and interannular hydrogen migrations
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The gas-phase reaction of p-Me3SiC6H4(CH2)3C6H5 (p-TSDPP) with gaseous cations, including C2H5+, Me2Cl+ and DCO+, has been studied in the pressure range from 10-8 to 103 Torr by Fourier-transform ion cyclotron resonance (FT-ICR) and by the radiolytic technique. The protonated or alkylated intermediates undergo intramolecular migration and intermolecular transfer of protons and/or Me3Si+. The results underline the role of the spectator ring in providing internal solvation to an arenium moiety, as evidenced by the noticeable stability towards Me3Si loss with respect to a single-ring model substrate, p-Me3SiC6H4Me (p-TST), upon reaction with the same gaseous ions. The extent of the alkylation route relative to the alkyldesilylation processes, measured as a function of the arenium ion lifetime, permits derivation of the rate constant for the conversion by proton transfer of the originally formed arenium ions to ipso-silylated isomers (k(i)). The estimated values of k(i(p-TST)) = 5 x 109 s-1 and k(i(p-TSDPP)) = 2 x 108 s-1 at 120°C suggest that interannular H shifts are faster than ring-to-ring H transfer, in agreement with previous evidence from tert-butylated arenium ions. The reactivity of [Me3Si=arene]+ adducts, adequately described by the Wheland σ-complex model, does not exclude the intermediacy of an ion-neutral noncovalent complex.
- Crestoni, Maria Elisa
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p. 993 - 999
(2007/10/03)
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- New deoxynojirimycin derivatives as potent inhibitors of intestinal α-glucohydrolases
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New N-alkyl, alkenyl and benzyl substituted DNJ derivatives incorporating a silicon atom in the substituent were synthesised. Kinetic parameters (K(i), t( 1/4 )) for inhibition of rat intestinal α-glucohydrolases as well as human lysosomal α-glucosidases
- Lesur, Brigitte,Ducep, Jean-Bernard,Lalloz, Marie-Noelle,Ehrhard, Anne,Danzin, Charles
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p. 355 - 360
(2007/10/03)
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- N-derivatives of 1-deoxy nojirimycin
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This invention relates to novel N-derivatives of 1-deoxy nojirimycin, to the method for their preparation and to their use in the treatment of diabetes and the use against retro-viruses, particularly in the treatment of acquired immuno-deficiency syndrome
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- The origin of regioselectivity in an allenyllithium reagent
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A pair of allenyl (5-methyl-4-(trimethylstannyl)-2,3-hexadiene, 1A-Sn) and propargyl (5-methyl-2-(trimethylstannyl)-3-hexyne, 1P-Sn) stannanes were prepared and used in a series of lithium-tin exchange experiments (both give the same lithium reagent, 1A-L
- Reich, Hans J.,Holladay, Johnathan E.,Mason, J. Derek,Sikorski, William H.
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p. 12137 - 12150
(2007/10/03)
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- Pulse Technique Pyrolysis of some Arylsilanes and Their Thermal Reactions with Aliphatic and Aromatic Alcohols Over Ni-Y-Zeolite
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p-Tolyltrimethylsilane and phenyltrimethylsilane were subjected in the gas phase to pyrolysis and thermolysis reactions with alcohols and phenols at different temperatures over Ni Y-zeolite using a pulse catalytic technique.The obtained alkoxy- and phenoxy-trimethylsilanes with other side products were identified by gas liquid chromatographic analysis.The yield in each case varied with the reaction temperature.The highest yield was obtained at 250 deg C.The different pathways of these thermolysis reactions are discussed and the results are assigned.
- Ramadan, N. A.,Abo-Elenin, O. M.,Badawi, A. M.
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- N-derivatives of 1-deoxy nojirimycin
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This invention relates to novel N-derivatives of 1-deoxy nojirimycin, to the method for their preparation and to their use in the treatment of diabetes and the use against retro-viruses, particularly in the treatment of acquired immuno-deficiency syndrome
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- The Electrochemical Reductive Trimethylsilylation of Aryl Chlorides: A Good Route to Aryltrimethylsilanes and a Novel Route to Tris(trimethylsilyl)cyclohexadienes
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The electroreductive trimethylsilylation of aryl chlorides R-C6H4Cl (R = H, o-Me, m-Me, p-Me) can be controlled so as to give, in good yields, either the corresponding aryltrimethylsilanes (products of the reduction of the carbon-chlorine bond) or mixtures of cis- and trans-tris(trimethylsilyl)cyclohexa-1,3(or 1,4)-dienes (products of the successive reduction of the carbon-chlorine bond and the partial reduction of the aromatic ring).Which of the two products is formed depends upon how much electricity is passed during the constant current electrolysis, in a one-compartment cell equipped with a sacrificial aluminum anode, of an aryl chloride in 80:20 THF/HMPA solution that also contains Et4NBF4 as the supporting electrolyte and excess Me3SiCl.The electroreductive trimethylsilylation of phenyltrimethylsilane gave, in 62percent yield, a mixture of three 3,5,6-tris(trimethylsilyl)cyclohexa-1,3-dienes, of which the trans, pseudo a-a isomer constituted 89percent.Such products cannot be obtained by the chemoreductive trimethylsilylation of phenyltrimethylsilane.The electroreductive trimethylsilylation of benzene and toluene produced the corresponding bis(trimethylsilyl)cyclohexa-1,4-dienes.The regio- and stereochemical outcomes of the electroreductive trimethylsilylation of the various substrates can be explained in terms of the electronic and steric effects of the substituents originally attached to the aromatic ring and the steric effects of the trimethylsilyl groups that are subsequently attached.
- Bordeau, Michel,Biran, Claude,Pons, Pierrette,Leger-Lambert, Marie-Pierre,Dunogues, Jacques
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p. 4705 - 4711
(2007/10/02)
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- Retinobenzoic Acids. 5. Retinoidal Activities of Compounds Having a Trimethylsilyl or Trimethylgermyl Group(s) in Human Promyelocytic Leukemia Cells HL-60
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The retinoidal activities of trimethylsilyl or trimethylgermyl-containing retinobenzoic acids are discussed on the basis of differentiation-inducing activity on human promyelocytic leukemia cells HL-60.Compounds with a trimethylsilyl or trimethylgermyl gr
- Yamakawa, Takeru,Kagechika, Hiroyuki,Kawachi, Emiko,Hashimoto, Yuichi,Shudo, Koichi
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p. 1430 - 1437
(2007/10/02)
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- Catalytic C-H Activation. Silylation of Arenes with Hydrosilane or Disilane by RhCl(CO)(PMe3)2 under Irradiation
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Direct silylation of arenes with triethylsilane or hexamethyldisilane were catalyzed by RhCl(CO)(PMe3)2 under irradiation.
- Sakakura, Toshiyasu,Tokunaga, Yuko,Sodeyama, Touru,Tanaka, Masato
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p. 2375 - 2378
(2007/10/02)
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