- Functional Group Variation in tert-Butyldiphenylsilanes (TBDPS): Syntheses, Reactivities, and Effects on the Intermolecular Interaction Pattern in the Molecular Crystalline State
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We present the preparation of tert-butyldiphenylsilanes differing in one functional group. The molecular structures of the phenyl (3), methoxy (4), and amino derivatives (5) were elucidated by single-crystal X-ray diffraction analysis and their crystal packing investigated by Hirshfeld surface analysis along with 2D fingerprint plots. In the all-C derivative 3, the high symmetry dependence of the crystal packing enables a multitude of directional C(methyl)?H???C(π) interactions between the tert-butyl and phenyl groups. The methoxy derivative 4 is characterized by considerably short H???H contacts possibly resulting from pre-orienting C(aryl)?H???O and C(aryl)?H???C(π) hydrogen bonds. In the amino derivative 5, the nitrogen atom is not involved in intermolecular interactions, instead dispersive H???H contacts might become more important for the crystal cohesion. These findings once again underline the pronounced lone electron pair density transfer from the nitrogen atom towards the silicon atom.
- Bauer, Jonathan O.,Espinosa-Jalapa, Noel Angel,Fontana, Nicolò,G?tz, Tobias,Falk, Alexander
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p. 2636 - 2642
(2021/06/17)
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- Neutral-Eosin-Y-Photocatalyzed Silane Chlorination Using Dichloromethane
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Chlorosilanes are versatile reagents in organic synthesis and material science. A mild pathway is now reported for the quantitative conversion of hydrosilanes to silyl chlorides under visible-light irradiation using neutral eosin Y as a hydrogen-atom-transfer photocatalyst and dichloromethane as a chlorinating agent. Stepwise chlorination of di- and trihydrosilanes was achieved in a highly selective fashion assisted by continuous-flow micro-tubing reactors. The ability to access silyl radicals using photocatalytic Si?H activation promoted by eosin Y offers new perspectives for the synthesis of valuable silicon reagents in a convenient and green manner.
- Fan, Xuanzi,Xiao, Pin,Jiao, Zeqing,Yang, Tingting,Dai, Xiaojuan,Xu, Wengang,Tan, Jin Da,Cui, Ganglong,Su, Hongmei,Fang, Weihai,Wu, Jie
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supporting information
p. 12580 - 12584
(2019/08/16)
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- METHOD FOR PRODUCING HALOSILANE COMPOUND HAVING TERTIARY HYDROCARBON GROUP
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PROBLEM TO BE SOLVED: To provide a method for producing a halosilane compound having a tertiary hydrocarbon group directly from a dialkyl halosilane without using a highly dangerous compound. SOLUTION: The method for producing a halosilane compound represented by formula (3) and having a tertiary hydrocarbon group is provided that includes: a first step of activating a Grignard reagent having a tertiary monovalent hydrocarbon group in the presence of a copper compound, and a lithium compound; and a second step of reacting the Grignard reagent activated by the first step with dialkyl dihalosilane represented by formula (2). In the formula, R1 is an unsubstituted 4-20C tertiary monovalent hydro carbon group, R2 is independently a substituted/unsubstituted 1C-20C monovalent hydrocarbon group, and X2 is independently a halogen. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0028-0031; 0033-0037
(2019/12/13)
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- Iron-catalyzed chlorination of silanes
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A simple and highly efficient iron-catalyzed method for the chlorination of silanes has been developed. By use of 0.5-2% of the Fe(III)-based catalyst FeCl3 or Fe(acac)3 in the presence of 1-1.5 equiv of acetyl chloride as the chlorine donor, a large number of silanes, alkoxysilanes, and silanols were converted to the corresponding chlorosilanes in 50-93% yields. In contrast to earlier reported methods often suffering from expensive catalysts or use of stoichiometric metal salts, hazardous reagents, and reaction conditions, the presently described methodology allows benign reaction conditions and simple workup while using only catalytic amounts of a readily available and economically viable iron catalyst.
- Savela, Risto,Zawartka, Wojciech,Leino, Reko
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experimental part
p. 3199 - 3206
(2012/06/04)
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- An atom-efficient and powerful method for direct esterification of silyl ethers catalyzed by HClO4-SiO2
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An efficient and convenient procedure for direct esterification of alkyl and aryl silyl ethers with Ac2O and a catalyst system of perchloric acid immobilized on a silica gel (HClO4-SiO2) has been developed. The silyl protecting groups are directly replaced by acetyls and the protecting groups themselves are transformed into acetates as the sole byproducts, which can be readily recovered and converted back to silylchlorides, the original protecting agents, thus minimizing wastes.
- Du, Ti-Jian,Wu, Qin-Pei,Liu, Hai-Xia,Chen, Xi,Shu, Yi-Nan,Xi, Xiao-Dong,Zhang, Qing-Shan,Li, Yun-Zheng
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scheme or table
p. 1096 - 1101
(2011/04/16)
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- Modular approach to silicon-bridged biaryls: Palladium-catalyzed intramolecular coupling of 2-(arylsilyl)aryl triflates
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(Chemical Equation Presented) Bridge of Si: Intramolecular direct arylation of 2-(arylsilyl)aryl triflates is catalyzed smoothly by Pd(OAc) 2/PCy3 in the presence of Et2NH in dimethylacetamide (DMA), giving rise to the corresponding silicon-bridged biaryls in good to excellent yields. The new approach has led to the synthesis of a silicon-bridged 2-phenylindole (see scheme) that exhibits blue photoluminescence in the solid state with extremely high quantum yields.
- Shimizu, Masaki,Mochida, Kenji,Hiyama, Tamejiro
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supporting information; body text
p. 9760 - 9764
(2009/05/30)
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- Fluorescein-based metal sensors, and methods of making and using the same
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The present invention is directed, in part, to fluorescein-based ligands for detection of metal ions, and methods of making and using the same.
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- Process for the preparation of silanes, with a tertiary hydrocarbon group in the a-position relative to the silicon atom
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The invention relates to a process for the preparation of silanes of the general formula 1 by reaction of Grignard reagents of the general formula 2 with silanes of the general formula 3 wherein R denotes C1 - to C10 -hydrocarbon radicals optionally substituted by fluorine, chlorine or cyano radicals, R1, in the α-position relative to the silicon atom, denotes tertiary C4 - to C30 -hydrocarbon radicals optionally substituted by fluorine, chlorine or cyano radicals, X and X1 each denote chlorine, bromine or iodine, m denotes the values 2 or 3 and n denotes the values 1 or 2, in the presence of a transition metal catalyst and an inert, aprotic, and chelating compound.
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- Synthesis of Some Carbocyclic Nucleoside Analogues Based on a Bicyclohexane Ring System
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The carbocyclic nucleoside analogues 11, 14, and 17 have been prepared from (endo-bicyclohept-2-en-6-yl)methanol.
- Gooding, H.,Roberts, Stanley M.,Storer, Richard
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p. 1891 - 1892
(2007/10/02)
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- The recycling of organosilyl protecting species used in organic synthesis and the water binding ability of the silanol tBuMe2SiOH
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The silanols formed on the cleavage of organosilyl protecting groups from organic compounds can be efficiently reconverted into the chlorosilanes used in the initial silylation reaction by treatment with SOCl2.The silanol tBuMe2SiOH is very readily removed from organic reaction mixtures as its remarkably volatile hemihydrate tBuMe2SiOH>2 * H2O.
- Lickiss, Paul D.,Stubbs, Katharine M.
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p. 171 - 174
(2007/10/02)
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- Preparation of tertiary-hydrocarbylsilyl compounds
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The present invention relates to a method for the preparation of tertiary-hydrocarbylsilyl compounds through a Grignard reaction. A Grignard reagent of formula RMgX, in which R is a tertiary-hydrocarbyl group and X is a halogen atom, is reacted with a silicon compound of formula R1a SiX4-a ; where R1 is a substituted or unsubstituted monovalent hydrocarbon group and a is an integer with a value of zero to three. The process is ran in the presence of a catalytic quantity of a cyano compound or a thiocyanate compound.
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- NOVEL AND FACILE SYNTHESES OF T-BUTYL SUBSTITUTED SILANES FROM T-BUTYL MAGNESIUM CHLORIDE AND CHLOROSILANES CATALYZED BY CUPROUS CYANIDE
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t-Butyl substituted silanes, e.g. t-butyldimethylchlorosilane, were successfully obtained by cuprous chloride promoted coupling reaction of t-butyl Grignard reagent and chlorosilanes.
- Shirahata, Akihiko
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p. 6393 - 6394
(2007/10/02)
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