- Enhancement in the gas permeabilities of novel polysulfones with pendant 4-trimethylsilyl-α-hydroxylbenzyl substituents
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A series of modified polymers with 4-trimethylsilyl-α-hydroxylbenzyl (HBTMS) substituents were made as new materials for membrane gas separation. HBTMS was introduced onto polysulfone (PSf), tetramethylpolysulfone (TMPSf), and hexafluoropolysulfone (6FPSf
- Dai, Ying,Guiver, Michael D.,Robertson, Gilles P.,Kang, Yong Soo,Lee, Kwi Jong
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Read Online
- Design of novel luminescent porphyrins bearing donor-acceptor groups
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In this work, we report the synthesis and characterization of a novel series of porphyrins, some of them bearing donor-acceptor groups. meso-substituted free-base porphyrins:5-(4-amino-phenyl)-10,15,20- triphenylporphyrin (TPPNH2) and 5-(4-acet
- Caicedo, Carolina,Zaragoza-Galán, Gerardo,Crusats, Joaquim,El-Hachemi, Zoubir,Martínez, Ana,Rivera, Ernesto
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Read Online
- Preparation method for synthesizing aryl aldehyde compounds by reducing aryl secondary amide or aryl secondary amide derivative through phenylsilane
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The invention provides a preparation method for synthesizing aryl aldehyde compounds by reducing an aryl secondary amide or aryl secondary amide derivative through phenylsilane. In an inert atmosphere, the aryl secondary amide or an aryl secondary amide derivative is used as a raw material, phenylsilane is used as a reducing agent, 1, 4-dioxane or tetrahydrofuran or diethyl ether is used as a solvent, under the action of isopropyl magnesium chloride, a reaction is performed for 12-48 h at 40-70 DEG C, quenching, separating and purification are performed after the reaction is completed, and the aryl aldehyde product is obtained. The whole preparation process realizes one-step conversion from aryl secondary amide to aryl aldehyde, has the advantages of low cost, mild reaction conditions and high reaction yield, and avoids the use of high-temperature harsh conditions and high-cost noble metal catalysts.
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Paragraph 0052-0056
(2021/11/10)
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- Design, Synthesis, and Implementation of Sodium Silylsilanolates as Silyl Transfer Reagents
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There is an increasing demand for facile delivery of silyl groups onto organic bioactive molecules. One of the common methods of silylation via a transition-metal-catalyzed coupling reaction employs hydrosilane, disilane, and silylborane as major silicon sources. However, the labile nature of the reagents or harsh reaction conditions sometimes render them inadequate for the purpose. Thus, a more versatile alternative source of silyl groups has been desired. We hereby report a design, synthesis, and implementation of storable sodium silylsilanolates that can be used for the silylation of aryl halides and pseudohalides in the presence of a palladium catalyst. The developed method allows a late-stage functionalization of polyfunctionalized compounds with a variety of silyl groups. Mechanistic studies indicate that (1) a nucleophilic silanolate attacks a palladium center to afford a silylsilanolate-coordinated arylpalladium intermediate and (2) a polymeric cluster of silanolate species assists in the intramolecular migration of silyl groups, which would promote an efficient transmetalation.
- Yamagishi, Hiroki,Saito, Hayate,Shimokawa, Jun,Yorimitsu, Hideki
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p. 10095 - 10103
(2021/08/18)
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- Metal- And additive-free C-H oxygenation of alkylarenes by visible-light photoredox catalysis
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A metal- and additive-free methodology for the highly selective, photocatalyzed C-H oxygenation of alkylarenes under air to the corresponding carbonyls is presented. The process is catalyzed by an imide-acridinium that forms an extremely strong photooxidant upon visible light irradiation, which is able to activate inert alkylarenes such as toluene. Hence, this is an easy to perform, sustainable and environmentally friendly oxidation that provides valuable carbonyls from abundant, readily available compounds.
- García Manche?o, Olga,Kuhlmann, Jan H.,Pérez-Aguilar, María Carmen,Piekarski, Dariusz G.,Uygur, Mustafa
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supporting information
p. 3392 - 3399
(2021/05/21)
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- Higher Carbon Analogues of 1,4-Dihydropyridines as Potent TGFβ/Smad Inhibitors
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The C to Si and Ge exchange in bioactive compounds has often led to positive changes in the molecular properties, whereby Ge analogues are underrepresented. This is only possible at tetrahedral positions, and it is necessary for the analogue building bloc
- Barth, Eva R.,L?ngle, Daniel,Wesseler, Fabian,Golz, Christopher,Krupp, Anna,Schade, Dennis,Strohmann, Carsten
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p. 176 - 181
(2020/01/03)
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- Synthesis and photostability of 1,4-bis(5-phenyloxazol-2-yl)benzene (POPOP) structural isomers and their trimethylsilyl derivatives
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In this work, a versatile synthetic method for preparation of linear phenyloxazoles and their organosilicon derivatives under mild conditions via a combination of van Leusen and direct C[sbnd]H arylation reactions is reported. It was used for the synthesi
- Skorotetcky, Maxim S.,Borshchev, Oleg V.,Surin, Nikolay M.,Odarchenko, Yaroslav,Pisarev, Sergey A.,Peregudova, Svetlana M.,T?rnroos, Karl W.,Chernyshov, Dmitry,Ivanov, Dimitri A.,Ponomarenko, Sergey A.
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p. 128 - 136
(2017/02/19)
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- Porphyrins with a carbosilane dendrimer periphery as synthetic components for supramolecular self-assembly
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The preparation of the shape-persistent carbosilane-functionalized porphyrins H2TPP(4-SiRR′Me)4, Zn(ii)-TPP(4- SiRR′Me)4 (R = R′ = Me, CH2CHCH2, CH2CH2CH2OH; R = Me, R
- Ishtaiwi, Zakariyya,Rueffer, Tobias,Klaib, Sami,Buschbeck, Roy,Walfort, Bernhard,Lang, Heinrich
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p. 7868 - 7888
(2014/05/20)
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- Gold-catalyzed oxidative coupling reactions with aryltrimethylsilanes
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During continuing studies with a novel oxidative gold oxyarylation reaction, arylsilanes were found to be competent coupling partners, providing further evidence for an intramolecular electrophilic aromatic substitution mechanism. While providing yields complementary to those of the previously described boronic acid methods, the use of trimethylsilanes reduces the observation of homocoupling byproducts and allows for facile intramolecular coupling reactions.
- Brenzovich Jr., William E.,Brazeau, Jean-Francois,Toste, F. Dean
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supporting information; experimental part
p. 4728 - 4731
(2010/12/25)
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- Heteroaryl carboxamide compounds
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Compounds of formula I their manufacture, pharmaceutical compositions containing them and their use as medicaments.
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Page/Page column 12
(2008/06/13)
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- Heteroaryl and benzyl amide compounds
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Compounds of formula I wherein R1, R2, R4, R5, A, B, D and n are as defined, and pharmaceutically acceptable salts thereof, processes for their preparation, their use as pharmaceuticals and pharmaceutical compositions comprising them.
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Page/Page column 9
(2010/11/28)
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- AMIDES AND METHOD FOR PLANT DISEASE CONTROL WITH THE SAME
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N-(α-cyanobenzyl)amide compounds represented by the formula (1): wherein R1 represents a hydrogen atom; a halogen atom; a C1-C6 alkyl group optionally substituted with a halogen atom or the like; or the like, R2 represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group or the like, R3 represents a hydrogen atom or the like, R4 represents a C1-C4 alkyl group, a C3-C4 alkenyl group or the like, R5 represents a C1-C4 alkyl group, a C3-C4 alkenyl group, or the like, R6 represents a hydrogen atom or the like, R7 represents a hydrogen atom or the like, R8 represents a hydrogen atom or the like, R9 represents a hydrogen atom or the like, R10 represents a hydrogen atom or the like, R11 represents a hydrogen atom or the like, and R12 represents a hydrogen atom or the like, have excellent control activities against plant diseases.
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Page/Page column 85
(2010/11/08)
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- A novel method for the synthesis of regiospecifically sulfonated porphyrin monomers and dimers
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A novel method has been developed to regiospecifically synthesize water-soluble sulfonated porphyrin monomers tetrakis(4′-sulfonatophenyl)porphyrin, tetrakis(3′-sulfonatophenyl)porphyrin, tetrakis(2′-sulfonatophenyl)porphyrin, tetrakis(2′,5′-dimethyl-4′-sulfonatophenyl)porphyrin, the dimers of 1,2-bis[5,10,15-tri(4′-sulfonatophenyl)porphyrinyl]benzene and 1,2-bis[5,10,15-tri(2′,5′-dimethyl-4′-sulfonatophenyl) porphyrinyl]benzene in high yields through introduction of the trimethylsilyl group on the phenyl rings and reaction with trimethylsilyl chlorosulfonate in CCl4 solvent.
- Ye, Bao-Hui,Naruta, Yosinori
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p. 3593 - 3601
(2007/10/03)
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- Process for the preparation of Grignard reagents and novel Grignard reagents
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Grignard reagents which contain a protected aldehyde function are obtained in a particularly advantageous manner from a halogenated aldehyde by reaction with a secondary monoamine to give an open-chain aminal, and conversion of the latter into a Grignard
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- Diphenylphosphinophenolate: A ligand for the palladium-catalysed silylation of aryl halides activating simultaneously both palladium and silicon
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Diphenylphosphinophenolate was found to be an effective ligand for the palladium-catalysed silylation of aryl halides, activating not only palladium but also silicon of a disilane, where aryl bromides and iodides having such substituents as methyl, methoxy, amino, ethoxycarbonyl, trifluoromethyl, formyl or phenyl are applicable to the reaction with hexamethyldisilane to give the corresponding trimethylsilylarenes.
- Shirakawa,Kurahashi,Yoshida,Hiyama
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p. 1895 - 1896
(2007/10/03)
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- Photochemistry of a trisilane substituted by a pendant p-cyanostilbene electron acceptor chromophore
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Photolysis of (E)-4-cyano-4'-(2-heptamethyltrisilanyl)stilbene (E)-3 in a medium polarity solvent (CH2Cl2) results in efficient intramolecular electron transfer, which converts the initial π,π* excited state (1LE state) to the charge transfer (CT) excited state. The CT excited state fluorescesces, undergoes E,Z photoisomerization, and reacts with MeOH to produce hydrosilane 4 via Si-Si bond cleavage and protonation of the central silicon, as shown by deuterium labeling. The CT excited state assignments are consistent with the observed quadratic plots of 1/Φ(f) versus [MeOH] and 1/Φ(EZ) versus [MeOH], which indicate that both the initial 1LE state and the CT excited state are quenched by MeOH, with the CT excited state serving as the emissive state and the state primarily responsible for the E,Z photoisomerization. Although biacetyl triplet sensitized photolysis results in efficient E,Z isomerization, quenching of direct photolyses by azulene shows (Z)-3 is not a product of the lowest energy triplet excited state, populated from the CT state by back electron transfer. The azulene quenching also shows that hydrosilane 4 is formed from the same excited state that gives (Z)-3. The intermediacy of a complex of the CT excited state with MeOH accounts for the observed upward curvature in the plot of 1/Φ(SiH) vs 1/[MeOH]. The linear behavior of Φ(EZ)/Φ(SiH) x [MeOH] versus 1/[MeOH] further suggests that this complex reacts with uncomplexed MeOH to give hydrosilane 4.
- Steinmetz, Mark G.,Luo, Chang,Liu, Gui
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p. 2057 - 2065
(2007/10/03)
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- Guanidinium and Amidinium Fungicides: A New Class of Crbocation Mimetic Ergosterol Biosynthesis Inhibitors
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A novel class of chemical has been designed with the aim of inhibiting the Δ14-reductase and Δ8-Δ7-isomerase enzymes in the ergosterol biosynthesis pathway in fungi. Use was made of knowledge about the mechanisms of both e
- Arnold, Mary L.,Duriatti, Albert D.,Jung, Michel,Katz, Ruth B.,Liebeschuetz, John W.
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p. 341 - 356
(2007/10/03)
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- Transmission of electronic effects via a SiMe2 spacer in 4-mono- and 4,4'-disubstituted diphenyldimethylsilanes: 29Si and 13C NMR spectroscopy and PM3 semi-empirical calculations
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Some 29Si and 13C NMR studies were performed of series of 4-substituted phenyltrimethylsilanes and 4-substituted and 4,4'-disubstituted diphenyldimethylsilanes.Within each series linear relationships are found between the chemical shifts and (a) the Hammett substituent constants ?p and (b) the PM3-calculated total atomic charges.It is inferred that the SiMe2 ?-type spacer weakly mediates substituent effects in the ground state via a bond polarization mechanism.A comparison with available data for 4-substituted and 4,4'-disubstituted diphenylmethanes shows that the SiMe2 group is a better transmitter of electronic effects that the CH2 group. Keywords: Silicon; 29Si NMR; 13C NMR; Substituent effects; MO calculations
- Walree, Cornelis A. van,Lauteslager, Xavier Y.,Wageningen, Andreas M. A. van,Zwikker, Jan W.,Jenneskens, Leonardus W.
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p. 117 - 126
(2007/10/02)
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- Insecticidal, acaricidal and fungicidal aminopyrimidines
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Compounds of the formula: STR1 wherein A, Q and R2 to R5 are as defined in the text, compositions containing them and methods for using them to control insects, acarids and fungi.
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